US4992403A - Catalysts for hydrotreating hydrocarbons and methods of preparing the same - Google Patents

Catalysts for hydrotreating hydrocarbons and methods of preparing the same Download PDF

Info

Publication number: US4992403A
Authority: US; United States
Prior art keywords: catalyst; group; carbon atoms; general formula; mercapto
Prior art date: 1988-08-19
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.): Expired - Lifetime

Application number

US07/394,560

Other languages

English (en)

Inventor

Yasuhito Takahashi

Tomio Kawaguchi

Shigeru Sakai

Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)

Sumitomo Metal Mining Co Ltd

Original Assignee

Sumitomo Metal Mining Co Ltd

Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)

1988-08-19

Filing date

1989-08-16

Publication date

1991-02-12

1988-08-19 Priority claimed from JP63206194A external-priority patent/JPH0256249A/ja

1988-09-08 Priority claimed from JP63225099A external-priority patent/JPH0271844A/ja

1988-09-13 Priority claimed from JP63229246A external-priority patent/JPH0278441A/ja

1988-09-13 Priority claimed from JP63229247A external-priority patent/JPH0278442A/ja

1988-09-19 Priority claimed from JP63234000A external-priority patent/JPH0283041A/ja

1989-08-16 Application filed by Sumitomo Metal Mining Co Ltd filed Critical Sumitomo Metal Mining Co Ltd

1989-08-16 Assigned to SUMITOMO METAL MINING COMPANY LIMITED reassignment SUMITOMO METAL MINING COMPANY LIMITED ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: KAWAGUCHI, TOMIO, SAKAI, SHIGERU, TAKAHASHI, YASUHITO

1991-02-12 Application granted granted Critical

1991-02-12 Publication of US4992403A publication Critical patent/US4992403A/en

2009-08-16 Anticipated expiration legal-status Critical

Status Expired - Lifetime legal-status Critical Current

Links

239000003054 catalyst Substances 0.000 title claims abstract description 165
229930195733 hydrocarbon Natural products 0.000 title claims abstract description 67
150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 67
238000000034 method Methods 0.000 title claims description 161
229910052751 metal Inorganic materials 0.000 claims abstract description 212
239000002184 metal Substances 0.000 claims abstract description 212
150000001875 compounds Chemical class 0.000 claims abstract description 118
NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 95
229910052782 aluminium Inorganic materials 0.000 claims abstract description 61
XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 61
150000002739 metals Chemical class 0.000 claims abstract description 58
125000000217 alkyl group Chemical group 0.000 claims abstract description 56
229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 48
239000000126 substance Substances 0.000 claims abstract description 47
-1 amino-substituted mercaptans Chemical class 0.000 claims abstract description 46
230000000737 periodic effect Effects 0.000 claims abstract description 46
HDFRDWFLWVCOGP-UHFFFAOYSA-N carbonothioic O,S-acid Chemical class OC(S)=O HDFRDWFLWVCOGP-UHFFFAOYSA-N 0.000 claims abstract description 39
239000002253 acid Substances 0.000 claims abstract description 35
RVEZZJVBDQCTEF-UHFFFAOYSA-N sulfenic acid Chemical class SO RVEZZJVBDQCTEF-UHFFFAOYSA-N 0.000 claims abstract description 31
150000002894 organic compounds Chemical class 0.000 claims abstract description 27
229910052783 alkali metal Inorganic materials 0.000 claims abstract description 26
229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 26
QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 21
150000001340 alkali metals Chemical class 0.000 claims abstract description 20
150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 20
239000004215 Carbon black (E152) Substances 0.000 claims abstract description 12
125000004432 carbon atom Chemical group C* 0.000 claims description 112
239000003795 chemical substances by application Substances 0.000 claims description 103
229910052717 sulfur Inorganic materials 0.000 claims description 97
NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 96
239000011593 sulfur Substances 0.000 claims description 96
239000000243 solution Substances 0.000 claims description 62
239000004411 aluminium Substances 0.000 claims description 59
125000001183 hydrocarbyl group Chemical group 0.000 claims description 55
CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 50
239000000203 mixture Substances 0.000 claims description 42
125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 39
DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 38
239000007864 aqueous solution Substances 0.000 claims description 35
FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical class O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 35
UFULAYFCSOUIOV-UHFFFAOYSA-N cysteamine Chemical compound NCCS UFULAYFCSOUIOV-UHFFFAOYSA-N 0.000 claims description 27
KOUKXHPPRFNWPP-UHFFFAOYSA-N pyrazine-2,5-dicarboxylic acid;hydrate Chemical compound O.OC(=O)C1=CN=C(C(O)=O)C=N1 KOUKXHPPRFNWPP-UHFFFAOYSA-N 0.000 claims description 27
PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 24
229910001593 boehmite Inorganic materials 0.000 claims description 24
DHBXNPKRAUYBTH-UHFFFAOYSA-N 1,1-ethanedithiol Chemical compound CC(S)S DHBXNPKRAUYBTH-UHFFFAOYSA-N 0.000 claims description 21
229910021446 cobalt carbonate Inorganic materials 0.000 claims description 21
ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 claims description 21
MKIJJIMOAABWGF-UHFFFAOYSA-N methyl 2-sulfanylacetate Chemical compound COC(=O)CS MKIJJIMOAABWGF-UHFFFAOYSA-N 0.000 claims description 20
LDTLDBDUBGAEDT-UHFFFAOYSA-N methyl 3-sulfanylpropanoate Chemical compound COC(=O)CCS LDTLDBDUBGAEDT-UHFFFAOYSA-N 0.000 claims description 18
125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 17
WCDSVWRUXWCYFN-UHFFFAOYSA-N 4-aminobenzenethiol Chemical compound NC1=CC=C(S)C=C1 WCDSVWRUXWCYFN-UHFFFAOYSA-N 0.000 claims description 15
UIJGNTRUPZPVNG-UHFFFAOYSA-N benzenecarbothioic s-acid Chemical compound SC(=O)C1=CC=CC=C1 UIJGNTRUPZPVNG-UHFFFAOYSA-N 0.000 claims description 15
229910044991 metal oxide Inorganic materials 0.000 claims description 14
150000004706 metal oxides Chemical class 0.000 claims description 14
BXAVKNRWVKUTLY-UHFFFAOYSA-N 4-sulfanylphenol Chemical compound OC1=CC=C(S)C=C1 BXAVKNRWVKUTLY-UHFFFAOYSA-N 0.000 claims description 13
WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 13
PJUIMOJAAPLTRJ-UHFFFAOYSA-N monothioglycerol Chemical compound OCC(O)CS PJUIMOJAAPLTRJ-UHFFFAOYSA-N 0.000 claims description 11
SOOARYARZPXNAL-UHFFFAOYSA-N 2-(Methylthio)phenol Chemical compound CSC1=CC=CC=C1O SOOARYARZPXNAL-UHFFFAOYSA-N 0.000 claims description 10
PVBRSNZAOAJRKO-UHFFFAOYSA-N ethyl 2-sulfanylacetate Chemical compound CCOC(=O)CS PVBRSNZAOAJRKO-UHFFFAOYSA-N 0.000 claims description 10
OWHSTLLOZWTNTQ-UHFFFAOYSA-N 2-ethylhexyl 2-sulfanylacetate Chemical compound CCCCC(CC)COC(=O)CS OWHSTLLOZWTNTQ-UHFFFAOYSA-N 0.000 claims description 8
DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims description 8
SMTOKHQOVJRXLK-UHFFFAOYSA-N butane-1,4-dithiol Chemical compound SCCCCS SMTOKHQOVJRXLK-UHFFFAOYSA-N 0.000 claims description 8
150000003568 thioethers Chemical class 0.000 claims description 7
150000003863 ammonium salts Chemical class 0.000 claims description 6
238000001035 drying Methods 0.000 claims description 6
238000005984 hydrogenation reaction Methods 0.000 claims description 6
229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 6
ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 6
LNRIEBFNWGMXKP-UHFFFAOYSA-N 2-ethylsulfanylethanol Chemical compound CCSCCO LNRIEBFNWGMXKP-UHFFFAOYSA-N 0.000 claims description 5
WBBPRCNXBQTYLF-UHFFFAOYSA-N 2-methylthioethanol Chemical compound CSCCO WBBPRCNXBQTYLF-UHFFFAOYSA-N 0.000 claims description 5
MJQWABQELVFQJL-UHFFFAOYSA-N 3-Mercapto-2-butanol Chemical compound CC(O)C(C)S MJQWABQELVFQJL-UHFFFAOYSA-N 0.000 claims description 5
GILAQKILVGHFPX-UHFFFAOYSA-N 3-ethylsulfanylpropane-1,2-diol Chemical compound CCSCC(O)CO GILAQKILVGHFPX-UHFFFAOYSA-N 0.000 claims description 5
FXIHXPKPLPKPJH-UHFFFAOYSA-N 3-methylsulfanylpropane-1,2-diol Chemical compound CSCC(O)CO FXIHXPKPLPKPJH-UHFFFAOYSA-N 0.000 claims description 5
QASBCTGZKABPKX-UHFFFAOYSA-N 4-(methylsulfanyl)phenol Chemical compound CSC1=CC=C(O)C=C1 QASBCTGZKABPKX-UHFFFAOYSA-N 0.000 claims description 5
APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 5
229940010552 ammonium molybdate Drugs 0.000 claims description 5
235000018660 ammonium molybdate Nutrition 0.000 claims description 5
239000011609 ammonium molybdate Substances 0.000 claims description 5
UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 5
229910001981 cobalt nitrate Inorganic materials 0.000 claims description 5
KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 5
CSJBSYKCAKKLKG-UHFFFAOYSA-N 2-ethylsulfanylphenol Chemical compound CCSC1=CC=CC=C1O CSJBSYKCAKKLKG-UHFFFAOYSA-N 0.000 claims 3
MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims 1
PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims 1
238000010438 heat treatment Methods 0.000 abstract description 10
JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 196
229910052750 molybdenum Inorganic materials 0.000 description 168
235000001508 sulfur Nutrition 0.000 description 96
238000006477 desulfuration reaction Methods 0.000 description 95
230000023556 desulfurization Effects 0.000 description 95
ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 85
239000010941 cobalt Substances 0.000 description 85
229910017052 cobalt Inorganic materials 0.000 description 85
GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 85
229910052961 molybdenite Inorganic materials 0.000 description 85
239000011733 molybdenum Substances 0.000 description 85
CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 85
229910052982 molybdenum disulfide Inorganic materials 0.000 description 85
OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 65
229910052698 phosphorus Inorganic materials 0.000 description 65
239000011574 phosphorus Substances 0.000 description 65
PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 25
XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
229910052759 nickel Inorganic materials 0.000 description 14
238000006243 chemical reaction Methods 0.000 description 13
229910052721 tungsten Inorganic materials 0.000 description 13
ZZTCCAPMZLDHFM-UHFFFAOYSA-N ammonium thioglycolate Chemical compound [NH4+].[O-]C(=O)CS ZZTCCAPMZLDHFM-UHFFFAOYSA-N 0.000 description 12
229940075861 ammonium thioglycolate Drugs 0.000 description 12
239000000843 powder Substances 0.000 description 12
239000001257 hydrogen Substances 0.000 description 11
229910052739 hydrogen Inorganic materials 0.000 description 11
UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 10
QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 9
VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 8
239000010937 tungsten Substances 0.000 description 8
229920001021 polysulfide Polymers 0.000 description 7
239000005077 polysulfide Substances 0.000 description 7
150000008117 polysulfides Polymers 0.000 description 7
FLDSMVTWEZKONL-AWEZNQCLSA-N 5,5-dimethyl-N-[(3S)-5-methyl-4-oxo-2,3-dihydro-1,5-benzoxazepin-3-yl]-1,4,7,8-tetrahydrooxepino[4,5-c]pyrazole-3-carboxamide Chemical compound CC1(CC2=C(NN=C2C(=O)N[C@@H]2C(N(C3=C(OC2)C=CC=C3)C)=O)CCO1)C FLDSMVTWEZKONL-AWEZNQCLSA-N 0.000 description 6
VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 description 6
230000000694 effects Effects 0.000 description 6
229910018404 Al2 O3 Inorganic materials 0.000 description 5
239000007788 liquid Substances 0.000 description 4
239000002994 raw material Substances 0.000 description 4
238000005987 sulfurization reaction Methods 0.000 description 4
QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 3
230000000052 comparative effect Effects 0.000 description 3
239000003085 diluting agent Substances 0.000 description 3
239000000377 silicon dioxide Substances 0.000 description 3
IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
150000001336 alkenes Chemical class 0.000 description 2
XFBXDGLHUSUNMG-UHFFFAOYSA-N alumane;hydrate Chemical compound O.[AlH3] XFBXDGLHUSUNMG-UHFFFAOYSA-N 0.000 description 2
ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 2
WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 2
229910052681 coesite Inorganic materials 0.000 description 2
238000007796 conventional method Methods 0.000 description 2
229910052906 cristobalite Inorganic materials 0.000 description 2
239000007789 gas Substances 0.000 description 2
150000002431 hydrogen Chemical class 0.000 description 2
229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
239000003960 organic solvent Substances 0.000 description 2
239000002574 poison Substances 0.000 description 2
231100000614 poison Toxicity 0.000 description 2
239000011148 porous material Substances 0.000 description 2
239000000047 product Substances 0.000 description 2
229910001388 sodium aluminate Inorganic materials 0.000 description 2
229910052682 stishovite Inorganic materials 0.000 description 2
229910052905 tridymite Inorganic materials 0.000 description 2
229910017344 Fe2 O3 Inorganic materials 0.000 description 1
LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
230000002378 acidificating effect Effects 0.000 description 1
239000004480 active ingredient Substances 0.000 description 1
WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
238000009835 boiling Methods 0.000 description 1
QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 1
125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
239000013065 commercial product Substances 0.000 description 1
229910052593 corundum Inorganic materials 0.000 description 1
239000010431 corundum Substances 0.000 description 1
230000018044 dehydration Effects 0.000 description 1
238000006297 dehydration reaction Methods 0.000 description 1
WMWXXXSCZVGQAR-UHFFFAOYSA-N dialuminum;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3] WMWXXXSCZVGQAR-UHFFFAOYSA-N 0.000 description 1
238000004821 distillation Methods 0.000 description 1
230000003028 elevating effect Effects 0.000 description 1
238000001125 extrusion Methods 0.000 description 1
238000010304 firing Methods 0.000 description 1
230000005484 gravity Effects 0.000 description 1
238000005470 impregnation Methods 0.000 description 1
239000012535 impurity Substances 0.000 description 1
229910052809 inorganic oxide Inorganic materials 0.000 description 1
229910000473 manganese(VI) oxide Inorganic materials 0.000 description 1
239000000463 material Substances 0.000 description 1
230000004048 modification Effects 0.000 description 1
238000012986 modification Methods 0.000 description 1
150000004682 monohydrates Chemical class 0.000 description 1
229910052757 nitrogen Inorganic materials 0.000 description 1
125000000962 organic group Chemical group 0.000 description 1
238000002161 passivation Methods 0.000 description 1
150000003016 phosphoric acids Chemical class 0.000 description 1
229920000642 polymer Polymers 0.000 description 1
238000003825 pressing Methods 0.000 description 1
239000002904 solvent Substances 0.000 description 1
239000007858 starting material Substances 0.000 description 1

Classifications

- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/20—Sulfiding
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
- C10G49/02—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used
- C10G49/04—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used containing nickel, cobalt, chromium, molybdenum, or tungsten metals, or compounds thereof

Definitions

the present invention relates to catalysts for hydrotreating hydrocarbons and to methods of preparing the same.
a catalyst composed of at least one metal selected from the metals of Group VI of the Periodic Table and the metals of Group VIII of the Periodic Table (the active component), such metals being carried on an inorganic oxide carrier such as alumina (Al 2 O 3 ), silica-alumina (SiO 2 -Al 2 O 3 ), titania (TiO 2 ) or the like, is employed.
an inorganic oxide carrier such as alumina (Al 2 O 3 ), silica-alumina (SiO 2 -Al 2 O 3 ), titania (TiO 2 ) or the like.
the Group VI metal molybdenum (Mo) and tungsten (W) are well utilized for the purpose, and as the Group VIII metal, cobalt (Co) and nickel (Ni) can be used.
Such a metal is generally carried on the carrier in the form of an oxide thereof, which, however, is an inactive compound. Accordingly, the catalyst must be activated by presulfurization so as to convert the metal oxide into the corresponding sulfide prior to being used in the hydrotreating reaction.
a sulfurizing agent is introduced into the catalyst layer, together with hydrogen, after the catalyst has been filled in a reactor where hydrotreating a hydrocarbon oil is to be effected.
the operating conditions for presulfurization vary in accordance with the hydrotreating process and with the sulfurizing agent used. For instance, where hydrogen sulfide is used as the sulfurizing agent, the compound is incorporated into hydrogen in an amount of from 0.5 to 5% by volume or so, and the hydrogen sulfide-containing hydrogen is applied to the catalyst in an amount of from 1000 to 3000 liters per liter of the catalyst (as calculated under the conditions of normal temperature and normal pressure) and the presulfurization is effected at 180° C.
the compound is diluted with a light hydrocarbon oil and is applied to the catalyst at a temperature of from 250° C. to 350° C., a pressure of from 20 to 100 kg/cm 2 , a liquid space velocity of from 0.5 to 2.0 hr -1 , and a hydrogen/oil ratio of from 200 to 1000 N-liter/liter.
the reaction system is substituted by a raw material oil which is actually to be processed and the intended hydrotreatment is started with the thus-activated catalyst.
the presulfurization has a significant influence on the success of the hydrotreatment to follow, pertinent selection of the materials to be employed in the process and careful operation of the process are required.
the agent must be a hydrocarbon oil free from olefins since olefins, if contained in the diluting agent, will form a polymer product and the product will poison the hydrotreating catalyst.
the catalyst metal would be passivated when reacted at a high temperature with hydrogen to be reduced.
This method is directed to presulfurization of an active metal-carried catalyst by impregnating the catalyst with a polysulfide of a general formula R-S(n)-R', where n represents an integer of from 3 to 20, and R and R' each represent a hydrogen atom or an organic group having from 1 to 150 carbon atoms per one molecule, and heat-treating the thus-impregnated catalyst at a temperature of 65° to 275° C. and a pressure of 0.5 to 70 bars and in the absence of hydrogen gas (Japanese Patent Application Laid-Open No. 61-111144).
the polysulfide as introduced into the catalyst sulfurizes the active metal by heat-treatment. Accordingly, where the above-mentioned presulfurization is carried out in a reactor, neither a sulfurizing agent nor a diluting agent is necessary and the operation is easy. In addition, the above-mentioned pre-sulfurization may also be effected even outside the reactor. In such a case, the presulfurized catalyst may be applied to the reactor, whereupon the intended hydrotreatment may immediately be started.
the amount of polysulfide used in the method is a stoichiometrical amount necessary for sulfurizing the whole active metal oxide (for example, CoO, MnO 3 ) in the catalyst by the successive heat-treatment thereof, and the polysulfide is diluted in a pertinent organic solvent and then applied to the catalyst for impregnation. Since the polysulfide is highly viscous, the viscosity would still be high even though it is diluted with an organic solvent and, as a result, there would be a problem that the polysulfide would hardly penetrate into the inside of fine pores of the catalyst.
the catalyst to be treated by presulfurization is prepared by a method where an aluminium hydrate obtained from a starting material of sodium aluminate is shaped, dried and fired to give a ⁇ -alumina, and the resulting ⁇ -alumina is impregnated with an aqueous solution of a water-soluble compound of an active metal and then dried and heat-treated so that the active metal is converted into the corresponding oxide form, or by a method where an aluminium hydrate is blended with an aqueous solution of a water-soluble compound of an active metal and then shaped, dried and fired so that the active metal is carried on a carrier composed of the resulting ⁇ -alumina in the form of the oxide form of the active metal.
the object of the present invention is to provide catalysts for hydrotreating of hydrocarbons which can be prepared more simply and more inexpensively than the above-mentioned conventional methods, which can be employed in hydrotreatment without pre-sulfurization, and which can be directly applied to hydrotreatment without heat treatment, as well as to provide methods for preparing such catalysts.
the present inventors have found that the object may be attained by employing a water-soluble compound of a metal of Group VI and Group VIII of the Periodic Table as the active ingredient together with employment of an organic compound having one or two sulfurs in place of polysulfides and further employing phosphoric acid.
the subject matter of the present invention is to provide a catalyst for hydrotreating of hydrocarbons which is composed of a carrier substance consisting essentially of an oxide of aluminium and/or an oxide hydrate of aluminium, at least one compound selected from water-soluble compounds of metals of Group VI and Group VIII of the Periodic Table and at least one organic compound selected from the group consisting of mercaptocarboxylic acids of a general formula:
n represents an integer of from 1 to 3; and R represents a hydrogen atom, or an alkali metal, an alkaline earth metal, an ammonium group, or an alkyl group having from 1 to 10 carbon atoms, thio-acids of a general formula:
R' represents a monovalent hydrocarbon group having from 1 to 15 carbon atoms, amino-substituted mercaptans of a general formula:
R" represents a divalent hydrocarbon group having from 1 to 5 carbon atoms, dimercaptans of a general formula:
R" represents a divalent hydrocarbon group having from 1 to 5 carbon atoms, and mercapto-alcohols of a general formula:
R"' represents a hydrocarbon group having from 1 to 15 carbon atoms
R a represents a hydrogen atom or an alkyl group having from 1 to 2 carbon atoms
n represents an integer of from 1 to 2.
the catalyst of the present invention is prepared by a method where a carrier substance consisting essentially of an oxide of aluminium and/or an oxide hydrate of aluminium is blended and kneaded with a solution containing at least one compound selected from water-soluble compounds of metals of Group VI and Group VIII of the Periodic Table and at least one organic compound selected from the group consisting of mercaptocarboxylic acids of a general formula:
n, R, R', R", R"' and R a have the same meanings as mentioned above, and the same shall apply hereunder.
the catalyst of the present invention is prepared by a method where a carrier substance consisting essentially of an oxide of aluminium and/or an oxide hydrate of aluminium is blended and kneaded with an aqueous solution of at least one compound selected from water-soluble compounds of metals of Group VI and Group VIII of the Periodic Table, the resulting blend is shaped and then temporarily dried, and the thus-dried and shaped body is impregnated with a solution of at least one organic compound selected from the group consisting of mercaptocarboxylic acids of a general formula:
the catalyst of the present invention is prepared by a method where a carrier substance consisting essentially of an oxide of aluminium and/or an oxide hydrate of aluminium is blended and kneaded with an aqueous solution of at least one organic compound selected from the group consisting of mercaptocarboxylic acids of a general formula:
the resulting blend is shaped and then temporarily dried, and the thus-dried and shaped body is impregnated with an aqueous solution of at least one compound selected from water-soluble compounds of metals of Group VI and Group VIII of the Periodic Table, and then again dried to prepare the catalyst.
a catalyst for hydrotreating hydrocarbons which comprises a shaped body of a mixture composed of a carrier substance consisting essentially of an oxide of aluminium and/or an oxide hydrate of aluminium, at least one compound selected from water-soluble compounds of metals of Group VI and Group VIII of the Periodic Table, a phosphoric acid, and at least one organic compound selected from the group consisting of mercapto-carboxylic acids of a general formula:
the catalyst of the fourth embodiment of the present invention is prepared by a method where a carrier substance consisting essentially of an oxide of aluminium and/or an oxide hydrate of aluminium is blended and kneaded with a solution containing at least one compound selected from water-soluble compounds of metals of Group VI and Group VIII of the Periodic Table, phosphoric acid and at least one organic compound selected from the group consisting of mercapto-carboxylic acids of a general formula:
the catalyst of the fourth embodiment of the present invention is prepared by a method where a carrier substance consisting essentially of an oxide of aluminium and/or an oxide hydrate of aluminium is blended and kneaded with an aqueous solution comprising at least one compound selected from water-soluble compounds of metals of Group VI and Group VIII of the Periodic Table and phosphoric acid, the resulting blend is shaped and then temporarily dried, and the thus-dried and shaped body is impregnated with a solution of at least one organic compound selected from the group consisting of mercapto-carboxylic acids of a general formula:
the catalyst of the fourth embodiment of the present invention is prepared by a method where a carrier substance consisting essentially of an oxide of aluminium and/or an oxide hydrate of aluminium is blended and kneaded with a solution comprising at least one compound selected from water-soluble compounds of metals of Group VI and Group VIII of the Periodic Table and at least one organic compound selected from the group consisting of mercapto-carboxylic acids of a general formula:
the resulting blend is shaped and then temporarily dried, and the thus-dried and shaped body is impregnated with an aqueous solution of phosphoric acid and then again dried to prepare the catalyst of the fourth embodiment of the present invention.
the catalyst of the fourth embodiment of the present invention is prepared by a method where a carrier substance consisting essentially of an oxide of aluminium and/or an oxide hydrate of aluminium is blended and kneaded with a solution containing phosphoric acid and at least one organic compound selected from the group consisting of mercapto-carboxylic acids of a general formula:
the resulting blend is shaped and then temporarily dried, and the thus-dried and shaped body is impregnated with an aqueous solution of at least one compound selected from water-soluble compounds of metals of Group VI and Group VIII of the Periodic Table and then again dried to prepare the catalyst of the fourth embodiment of the present invention.
the catalyst of the fourth embodiment of the present invention is prepared by a method where a carrier substance consisting essentially of an oxide of aluminium and/or an oxide hydrate of aluminium is blended and kneaded with an aqueous solution of at least one compound selected from water-soluble compounds of metals of Group VI and Group VIII of the Periodic Table, the resulting blend is shaped and then temporarily dried, and the thus-dried and shaped body is impregnated with a solution containing phosphoric acid and at least one organic compound selected from the group consisting of mercapto-carboxylic acids of a general formula:
the catalyst of the fourth embodiment of the present invention is prepared by a method where a carrier substance consisting essentially of an oxide of aluminium and/or an oxide hydrate of aluminium is blended and kneaded with a solution of at least one organic compound selected from the group consisting of mercapto-carboxylic acids of a general formula:
the resulting blend is shaped and then temporarily dried, and the thus-dried and shaped body is impregnated with an aqueous solution containing at least one compound selected from water-soluble compounds of metals of Group VI and Group VIII of the Periodic Table and phosphoric acid, and then again dried to prepare the catalyst of the fourth embodiment of the present invention.
the catalyst of the fourth embodiment of the present invention is prepared by a method where a carrier substance consisting essentially of an oxide of aluminium and/or an oxide hydrate of aluminium is blended and kneaded with an aqueous solution of phosphoric acid, the resulting blend is shaped and then temporarily dried, and the thus-dried and shaped body is impregnated with a solution containing comprising at least one compound selected from water-soluble compounds of metals of Group VI and Group VIII of the Periodic Table and at least one organic compound selected from the group consisting of mercapto-carboxylic acids of a general formula:
a carrier substance for use in the present invention which consists essentially of an oxide of aluminium and/or an oxide hydrate of aluminium
a ⁇ -alumina or boehmite obtainable by heat-treating a hydrate of aluminium is employed.
Boehmite has a structural formula of A10(OH) or a chemical formula of Al 2 O 3 .H 2 O as monohydrate of alumina), which is an aluminium oxide hydrate.
Boehmite is also prepared as a natural boehmite ore, which contains impurities of SiO 2 , FeO 2 , Fe 2 O 3 , MgO, CaO, etc.
boehmite When heated, boehmite is dehydrated to ⁇ -alumina, to ⁇ -alumina and to ⁇ -alumina in order, and this finally becomes ⁇ -alumina (corundum) at 1100° to 1200° C. Accordingly, as boehmite is an intermediate between aluminium hydroxide and aluminium oxide, it may be employed singly or it may also be employed in combination with an active ⁇ -alumina. Alternatively, only ⁇ -alumina may also be employed as the carrier substance. In addition, silica or titania may be blended with the noted compound and the resulting mixture may also be used as the carrier substance.
molybdenum (Mo) and tungsten (W) which are generally employed as active metals of catalysts are preferably employed in the form of ammonium molybdate and ammonium tungstate, respectively.
molybdenum trioxide and tungsten trioxide are employed, ammonia gas is applied thereto and they are used in the form of ammonium molybdate and ammonium tungstate.
cobalt (Co) and nickel (Ni) which are generally employed as active metals of catalysts are preferably employed in the form of cobalt nitrate, cobalt carbonate, nickel nitrate and nickel carbonate. They are used singly or in combination, in the form of an aqueous solution.
water-soluble compounds of the active metals are heated together with at least one of mercapto-carboxylic acids of a general formula HS--(CH 2 ) n --COOR, thio-acids of a general formula R'--COSH, amino-substituted mercaptans of a general formula H 2 N--R'--SH, dimercaptans of a general formula HS--R"--SH and mercapto-alcohols of a general formula R a S--R"'--(OH) n (hereinafter referred to as "mercapto-carboxylic acids and other sulfurizing agents")
they form sulfides such as MoS 2 , WS 2 , CoS, NiS and the like which are highly active in hydrogenation reactions.
the portion which is functional to sulfurization of active metals comprises one or two sulfur components in the molecule of the respective sulfurizing agent compounds. Accordingly, where the number of the carbon atoms in the hydrocarbon group in the molecule of the sulfurizing agent compound is large, the portion which is functional as the sulfurizing agent in the molecule would thereby be relatively small and, as a result, not only the compound is uneconomical, but also the compound would unfavorably bring superfluous carbons and hydrogens into the catalyst. Because of this, the sulfurizing compounds to be employed in the present invention are preferred to have as few carbon atoms as possible. Specifically, the number of carbon atoms in the compounds is preferably at most 15.
mercapto-carboxylic acids of a general formula HS--(CH 2 ) n --COOR where n represents an integer of from 1 to 3; and R represents a hydrogen atom, or an alkali metal, an alkaline earth metal, an ammonium group, or an alkyl group having from 1 to 10 carbon atoms
mercaptoacetic acid HSCH 2 COOH
⁇ -mercapto-propionic acid HSCH 2 CH 2 COOH
alkali metal salts, alkaline earth metal salts and ammonium salts thereof can be employed.
metal ion-free acid-type and ammonium salt-type compounds which do not form any substances that would poison the catalyst for hydrogenation reaction are preferred. These can be used also together with phosphoric acid in the form of a phosphoric acid-containing acidic aqueous solution.
mercaptocarboxylic acid esters such as methyl mercapto-acetate (HSCH 2 COOCH 3 ), ethyl 2-mercapto-acetate (HSCH 2 COOC 2 H 5 ), 2-ethylhexyl mercapto-acetate (HSCH 2 COOCH 8 H 17 ) or methyl 3-mercaptopropionate (HSCH 2 CH 22 COOCH 3 ).
thio-acids of a general formula R'--COSH where R' represents a hydrocarbon group having from 1 to 15 carbon atoms
R' represents a hydrocarbon group having from 1 to 15 carbon atoms
amino-substituted mercaptans of a general formula H 2 N--R"--SH where R" represents a divalent hydrocarbon group
2-aminoethane-thiol H 2 NCH 2 CH 2 SH
4-aminothiophenol H 2 NC 6 H 4 SH
dimercaptans of a general formula HS--R"--SH (where R" represents a divalent hydrocarbon group having from 1 to 15 carbon atoms, for example, there are mentioned ethanedithiol (HSCH 2 CH 2 SH) and 1,4-butanedithiol (HS(CH 2 ) 4 SH).
R a S--R"'--(OH) n (where R"' represents an alkyl group having from 1 to 15 carbon atoms or a phenyl group; R a represents a hydrogen atom or an alkyl group having from 1 to 2 carbon atoms; and n represents an integer of from 1 to 2)
2-mercaptoethanol HSCH 2 CH 2 OH
2-(methylthio)ethanol CH 3 SCH 2 CH 2 OH
2-(ethylthio)ethanol C 2 H 5 SCH 2 CH 2 OH
3-mercapto-2-butanol (CH 3 CH(SH)CH(OH)CH 3 ), 4-mercaptophenol (HSC 6 H 4 OH), 2-(methylthio)phenol (CH 3 SC 6 H 4 OH), 4-(methylthio)-phenol (CH 3 SC 6 H 4 OH), 2-ethylthio)phenol (C 2 H 5 SC 6 H 4 OH), 3-
the content of the metals of Group VI and Group VIII of the Periodic Table in the catalyst is preferred to fall within the range of from 1 to 30% by weight as the oxide of the active metal.
the catalyst contains both the metal of Group VI and the metal of Group VIII in combination, it is preferred that the content of the metal of Group VI is from 5 to 30% by weight and that of the metal of Group VIII is from 1 to 8% by weight, both as oxides of the metals.
the amount of the mercapto-carboxylic acids and other sulfurizing agents to be used in accordance with the present invention is preferably from 1 to 3 equivalents to the sulfur amount necessary for forming sulfides, which are highly active in hydrogenation reaction, such as MoS 2 , WS 2 , CoS or NiS, from the metals of Group VI and Group VIII of the Periodic Table. If the amount is less than one equivalent, a sufficient activity cannot be attained. On the other hand, if it is more than three equivalents, the activity is not enhanced. Accordingly, the amount falling within the noted range is best.
Phosphoric acid may be incorporated into the catalyst in an amount of about 3% by weight as P 2 O 5 .
the catalyst of the present invention can be prepared from the above-mentioned raw materials in the proportion as mentioned above, in accordance with the methods mentioned below.
the carrier substance, the active metal and the sulfurizing agent are kneaded, shaped and dried (Method I).
the carrier substance and the active metal are blended, shaped and dried, and the dried and shaped body is impregnated with the sulfurizing agent solution and re-dried (Method II).
the carrier substance and the sulfurizing agent are kneaded, shaped and dried, and the dried and shaped body is impregnated with the active metal solution and re-dried (Method III).
the carrier substance, the active metal, phosphoric acid and the sulfurizing agent are kneaded, shaped and dried (Method IV).
the carrier substance, the active metal and phosphoric acid are kneaded, shaped and dried, and the dried and shaped body is impregnated with the sulfurizing agent solution and re-dried (Method V).
the carrier substance, the active metal and the sulfurizing agent are kneaded, shaped and dried, and the dried and shaped body is impregnated with phosphoric acid solution and re-dried (Method VI).
the carrier substance, phosphoric acid and the sulfurizing agent are kneaded, shaped and dried, the dried and shaped body is impregnated with the active metal solution and re-dried (Method VII).
the carrier substance and the active metal are kneaded, shaped and dried, and the dried and shaped body is impregnated with a solution containing phosphoric acid and the sulfurizing agent and then re-dried (Method VIII).
the carrier substance and the sulfurizing agent are kneaded, shaped and dried, and the dried and shaped body is impregnated with a solution containing the active metal and phosphoric acid and then re-dried (Method IX).
the carrier substance and phosphoric acid are kneaded, shaped and dried, and the dried and shaped body is impregnated with a solution containing the active metal and the sulfurizing agent and then re-dried (Method X).
the drying temperature in the methods preferably falls within the range of from 50° to 200° C.; and the drying time therein preferably falls within the range of from 2 to 20 hours.
the freshly dried catalyst may be filled in a reactor column and can be utilized for hydrotreating a hydrocarbon oil in the column.
the water content in the catalyst as introduced thereinto in the course of the step of preparing the catalyst may be dried and removed therefrom after the catalyst has been put in the reactor column.
the catalyst of the present invention contains the mercapto-carboxylic acid and other sulfurizing agent in the form as carried on the carrier substance together with the watersoluble compound of the active metal, the active metal can be converted into the sulfide thereof in the course of the step of elevating the temperature of the reaction system up to the reaction temperature for dehydration and desulfurization of the hydrocarbon oil to be processed with the catalyst and, as a result, the catalyst can directly be utilized in the hydrodesulfurization for the hydrocarbon oil without presulfurization of the catalyst.
the catalysts of the present invention have a higher activity than the conventional catalysts which require presulfurization.
the reason is believed to be that the mercapto-carboxylic acids and other sulfurizing agents form a soluble coordination compound (metal mercaptide) together with the water-soluble compounds of the active metals and the resulting soluble coordinate compound is carried on the carrier substance in a highly dispersed form.
the catalyst activity was evaluated on the basis of hydrodesulfurization of Kuwait straight-run light gas oil (KSRLGO).
the KSRLGO used in the reaction had the following properties:
the reaction was effected by the use of a flow method reaction device, under the following reaction conditions.
the oil being processed was sampled every two hours, and the sulfur content in the oil and the desulfurization percentage were obtained.
the desulfurization percentage as mentioned in the following examples indicates an average of the values of the desulfurization percentage as obtained from the sulfur content in the processed oil as sampled four hours, six hours and eight hours after the start of the reaction.
the metal mercaptide solution and 272 g of spray-dried boehmite powder (Al 2 O 3 : 73.5 wt. %) were put in a kneader and kneaded to obtain a blend, which was then shaped.
the shaped body was dried at 100° C. for 16 hours to prepare a catalyst (Catalyst-1).
the breaking strength of Catalyst-1 was 1.5 kg/mm or more.
the molybdenum content was 15% by weight as MoO 3
the cobalt content was 4% by weight as CoO.
the amount of ammonium thioglycolate was contained 1.5 times the theoretical amount of sulfur necessary to convert Mo and Co into MoS 2 and CoS, respectively.
the desulfurization percentage with Catalyst-1 was 84.1%.
the metal mercaptide solution and 272 g of the same spray-dried boehmite powder as that used in Example 1 were put in a kneader and kneaded to obtain a blend, which was then shaped.
the shaped body was dried at 100° C. for 16 hours to prepare a catalyst (Catalyst-2).
the breaking strength of Catalyst-2 was 1.5 kg/mm or more.
the tungsten content was 15% by weight as WO 3
the cobalt content was 4% by weight as CoO.
the amount of ammonium thioglycolate used contained 1.5 times the theoretical amount of sulfur necessary to convert W and Co in to WS 2 and CoS, respectively.
the desulfurization percentage with Catalyst-2 was 83.0%.
aqueous solution 400 ml of an aqueous solution (pH 8.0) was prepared from 37.0 g of molybdenum trioxide, 15.8 g of cobalt carbonate (Co content: 49.1 wt. %), ammonia gas and water.
the shaped body was dried for 16 hours at 100° C. Next, the dried body was impregnated with 120 ml of an aqueous solution containing 109.1 g of mercapto-acetic acid and then dried for 16 hours at 100° C. Accordingly, Catalyst-3 was prepared.
the breaking strength of Catalyst-3 was 1.5 kg/mm or more.
the molybdenum content was 15% by weight as MoO 3 and the cobalt content was 4% by weight as CoO.
the amount of mercapto-acetic acid used contained 1.5 times the theoretical amount of sulfur necessary to convert Mo and Co into MoS 2 and CoS, respectively.
the desulfurization percentage with Catalyst-3 was 82.9%.
the shaped body was dried at 100° C. for 16 hours.
the dried, shaped body was then completely dipped in 150 ml of a solution prepared from 37.0 g of molybdenum trioxide, 15.8 g of cobalt carbonate (Co content: 49.1 wt. %), ammonia gas and water (pH 7.5) and thereafter dried at 100° C. for 16 hours.
the noted operation was repeated twice, and accordingly Catalyst-4 was prepared.
the breaking strength of Catalyst-4 was 1.5 kg/mm or more.
the molybdenum content was 15% by weight as MoN 3 and the cobalt content was 4% by weight as CoO.
the amount of ammonium thioglycolate used contained 1.5 times the theoretical amount of sulfur necessary to convert Mo and Co into MoS 2 and CoS, respectively.
the desulfurization percentage with Catalyst-4 was 83.6%.
the metal mercaptide solution and 673 g of dehydrated boehmite (Al 2 O 3 : 29.7 wt. %) were put in a heating kneader and kneaded with heating at 95° C. so as to evaporate the excess water, to obtain a blend, which was then shaped.
the shaped body was dried at 100° C. for 16 hours to obtain a catalyst (Catalyst-5).
Catalyst-6 and Catalyst-7 were prepared in the same manner as above, except that mercapto-acetic acid was used in an amount of 109.1 g and 145.5 g, respectively.
the breaking strength of Catalysts 5, 6 and 7 was 1.5 kg/mm or more.
the molybdenum content was 15% by weight as MoO 3
the cobalt content was 4% by weight as CoO
the phosphorus content is 3% by weight as P 2 O 5 .
the amount of mercapto-acetic acid used contained 1.0 times, 1.5 times and 2.0 times, respectively, the theoretical amount of sulfur necessary to convert Mo and Co into MoS 2 and CoS, respectively.
the desulfurization percentage with each of Catalysts 5, 6 and 7 was 82.5%, 83.5% and 82.0%, respectively.
109.1 g of mercapto-acetic acid was added to 300 ml of a solution prepared from 38.5 g of molybdenum trioxide, 16.4 g of cobalt carbonate (Co content: 49.1 wt. %), 12.5 g of 85 wt. % phosphoric acid and water, to obtain a phosphoric acid-containing metal mercaptide solution (pH 0.6).
the metal mercaptide solution and 272 g of the same spray-dried boehmite powder as that used in Example 1 were put in a kneader and kneaded to obtain a blend, which was then shaped.
the shaped body was dried at 100° C. for 16 hours to prepare a catalyst (Catalyst-8).
the breaking strength of Catalyst-8 was 1.5 kg/mm or more.
the molybdenum content was 15% by weight as MoO 3
the cobalt content was 4% by weight as CoO
the phosphorus content was 3% by weight as P 2 O 5 .
the amount of mercapto-acetic acid used contained 1.5 times the theoretical amount of sulfur necessary to convert Mo and Co into MoS 2 and CoS, respectively.
109.1 g of mercapto-acetic acid was added to 300 ml of a solution prepared from 38.5 g of molybdenum trioxide, 16.4 g of cobalt carbonate (Co content: 49.1 wt. %), 12.5 g of 85 wt. % phosphoric acid and water, to obtain a phosphoric acid-containing metal mercaptide solution (pH 0.6).
the metal mercaptide solution and 200 g of ⁇ -alumina powder were put in a kneader and kneaded to obtain a blend comprising the noted ⁇ -alumina and metal mercaptide. This was thereafter shaped.
the shaped body was dried at 100° C. for 16 hours to prepare a catalyst (Catalyst-9).
the breaking strength of Catalyst-9 was 1.5 kg/mm or more.
the molybdenum content was 15% by weight as MoO 3
the cobalt content was 4% by weight as CoO
the phosphorus content was 3% by weight as P 2 O 5 .
the amount of mercapto-acetic acid used contained 1.5 times the theoretical amount of sulfur necessary to convert Mo and Co into MoS 2 and CoS, respectively.
the desulfurization percentage with Catalyst-9 was 81.5%.
mercapto-propionic acid was added to 300 ml of a solution prepared from 38.5 g of molybdenum trioxide, 16.4 g of cobalt carbonate (Co content: 49.1 wt. %), 12.5 g of 85 wt. % phosphoric acid and water, to obtain a phosphoric acid-containing metal mercaptide solution (pH 0.7).
the metal mercaptide solution and 673 g of the same dehydrated boehmite as that used in Examples 5, 6 and 7 were put in a heating kneader and kneaded with heating at 95° C. so as to evaporate the excess water therefrom, to obtain a blend, which was then shaped.
the shaped body was dried at 100° C. for 16 hours to prepare a catalyst (Catalyst-10).
the breaking strength of Catalyst-10 was 1.5 kg/mm or more.
the molybdenum content was 15% by weight as MoO 3
the cobalt content was 4% by weight as CoO
the phosphorus content was 3% by weight as P 2 O 5 .
the amount of mercapto-propionic acid used contained 1.5 times the theoretical amount of sulfur necessary to convert Mo and Co into MoS 2 and CoS, respectively.
the desulfurization percentage with Catalyst-10 was 86.0%.
the metal mercaptide solution and 673 g of the same dehydrated boehmite as that used in Examples 5, 6 and 7 were put in a heating kneader and kneaded with heating at 95° C. so as to evaporate the excess water therefrom, to obtain a blend, which was then shaped.
the shaped body was dried at 100° C. for 16 hours to prepare a catalyst (Catalyst-11).
the breaking strength of Catalyst-11 was 1.5 kg/mm or more.
the molybdenum content was 15% by weight as MoO 3
the cobalt content was 4% by weight as CoO
the phosphorus content was 3% by weight as P 2 O 5 .
the amount of ammonium thioglycolate used contained 1.5 times the theoretical amount of sulfur necessary to convert Mo and Co into MoS 2 and CoS, respectively.
the desulfurization percentage with Catalyst-11 was 83.4%.
the metal mercaptide solution and 272 g of the same spray-dried boehmite powder as that used in Example 1 were put in a kneader and kneaded to obtain a blend, which was then shaped.
the shaped body was dried at 100° C. for 16 hours to prepare a catalyst (Catalyst-12).
the breaking strength of Catalyst-12 was 1.5 kg/mm or more.
the molybdenum content was 15% by weight as MoO 3
the nickel content was 4% by weight as NiO
the phosphorus content was 6.5% by weight as P 2 O 5 .
the amount of mercapto-acetic acid used contained 1.5 times the theoretical amount of sulfur necessary to convert Mo and Ni into MoS 2 and NiS, respectively.
the desulfurization percentage with the catalyst was 84.2%.
aqueous solution 400 ml of an aqueous solution (pH 2.0) was prepared from 38.5 g of molybdenum trioxide, 16.4 g of cobalt carbonate (Co content: 49.1 wt. %), 12.5 g of 85 wt. % phosphoric acid and water.
the shaped body was dried at 100° C. for 16 hours. Next, the dried body was completely impregnated with 150 ml of an aqueous solution containing 109.1 g of mercapto-acetic acid and then again dried at 100° C. for 16 hours. Accordingly, Catalyst-13 was prepared.
the breaking strength of Catalyst-13 was 1.5 kg/mm or more.
the molybdenum content was 15% by weight as MoO 3
the cobalt content was 4% by weight as CoO
the phosphorus content is 3% by weight as P 2 O 5 .
the amount of mercapto-acetic acid used contained 1.5 times the theoretical amount of sulfur necessary to convert Mo and Co into MoS 2 and COS, respectively.
the desulfurization percentage with Catalyst-13 was 77.8%.
the metal mercaptide solution and 272 g of the same spray-dried boehmite powder as that used in Example 1 were put in a kneader and kneaded to obtain a blend, which was then shaped.
the shaped body was dried at 100° C. for 16 hours. Next, the dried body was completely impregnated with 50 ml of an aqueous solution containing 12.5 g of 85 wt. % phosphoric acid and then again dried at 100° C. for 16 hours. Accordingly, Catalyst-14 was prepared.
the breaking strength of Catalyst-14 was 1.5 kg.mm or more.
the molybdenum content was 15% by weight as MoO 3
the cobalt content was 4% by weight as CoO
the phosphorus content was 3% by weight as P 2 O 5 .
the amount of ammonium thioglycolate used contained 1.5 times the theoretical amount of sulfur necessary to convert Mo and Co into MoS 2 and CoS, respectively.
the desulfurization percentage with Catalyst-14 was 82.8%.
the shaped body was dried at 100° C. for 16 hours.
the dried body was completely impregnated with 150 ml of a solution (pH 7.5) prepared from 38.5 g of molybdenum trioxide, 16.4 g of cobalt carbonate (Co content: 49.1 wt. %), ammonia gas and water and then again dried at 100° C. for 16 hours. Accordingly, Catalyst-15 was prepared.
the breaking strength of Catalyst-15 was 1.5 kg/mm or more.
the molybdenum content was 15% by weight as MoO 3
the cobalt content was 4% by weight as CoO
the phosphorus content was 3% by weight as P 2 O 5 .
the amount of mercapto-acetic acid used contained 1.5 times the theoretical amount of sulfur necessary to convert Mo and Co into MoS 2 and CoS, respectively.
the desulfurization percentage with Catalyst-15 was 83.5%.
the shaped body was dried at 100° C. for 16 hours. Next, the dried body was completely impregnated with 200 ml of an aqueous solution containing 12.5 g of 85 wt. % phosphoric acid and 109.1 g of mercapto-acetic acid and then again dried at 100° C. for 16 hours. Accordingly, Catalyst-16 was prepared.
the breaking strength of Catalyst-16 was 1.5 kg/mm or more.
the molybdenum content was 15% by weight as MoO 3
the cobalt content was 4% by weight as CoO
the phosphorus content was 3% by weight as P 2 O 5 .
the amount of mercapto-acetic acid used contained 1.5 times the theoretical amount of sulfur necessary to convert Mo and Co into MoS 2 and CoS, respectively.
the desulfurization percentage with Catalyst-16 was 83.2%.
the dried shaped body was completely impregnated with 100 ml of a solution (pH 2.0) prepared from 38.5 g of molybdenum trioxide, 16.4 g of cobalt carbonate (Co content: 49.1 wt. %), 12.5 g of 85 wt. % phosphoric acid and water and then again dried at 100° C. for 16 hours. Accordingly, Catalyst-17 was prepared.
the breaking strength of Catalyst-17 was 1.5 kg/mm or more.
the molybdenum content was 15% by weight as MoO 3
the cobalt content was 4% by weight as CoO
the phosphorus content was 3% by weight as P 2 O 5 .
the amount of mercapto-acetic acid used contained 1.5 times the theoretical amount of sulfur necessary to convert Mo and Co into MoS 2 and CoS, respectively.
the desulfurization percentage with Catalyst-17 was 84.2%.
the shaped body was dried at 100° C. for 16 hours.
the dried and shaped body was completely impregnated with 250 ml of a solution (pH 6.2) or a metal mercaptide obtained by adding 219.6 g of ammonium thioglycolate to a solution prepared from 38.5 g of molybdenum trioxide, 16.4 g of cobalt carbonate (Co content: 49.1 wt. %), ammonia gas and water, and then again dried at 100° C. for 16 hours. Accordingly, Catalyst-18 was prepared.
a solution pH 6.2
a metal mercaptide obtained by adding 219.6 g of ammonium thioglycolate to a solution prepared from 38.5 g of molybdenum trioxide, 16.4 g of cobalt carbonate (Co content: 49.1 wt. %), ammonia gas and water, and then again dried at 100° C. for 16 hours. Accordingly, Catalyst-18 was prepared.
the breaking strength of Catalyst-18 was 1.5 kg/mm or more.
the molybdenum content was 15% by weight as MoO 3
the cobalt content was 4% by weight as CoO
the phosphorus content was 3% by weight as P 2 O 5 .
the amount of ammonium thioglycolate used contained 1.5 times the theoretical amount of sulfur necessary to convert Mo and Co into MoS 2 and CoS, respectively.
the desulfurization percentage with Catalyst-18 was 83.0%.
Catalyst-19 was prepared in the same manner as Example 1, except that 102.7 g of methyl mercapto-acetate was used as the sulfurizing agent.
the breaking strength of Catalyst-19 was 1.5 kg/mm or more.
the molybdenum content was 15% by weight as MoO 3 and the cobalt content was 4% by weight as CoO.
the amount of methyl mercaptoacetate used contained 1.5 times the theoretical amount of sulfur necessary to convert Mo and Co into MoS 2 and CoS, respectively.
the desulfurization percentage with Catalyst-19 was 82.7%.
Catalyst-20 was prepared in the same manner as Example 2, except that 71.7 g of methyl mercapto-acetate was used as the sulfurizing agent.
the breaking strength of Catalyst-20 was 1.5 kg/mm or more.
the tungsten content was 15% by weight as WO 3 and the cobalt content was 4% by weight as CoO.
the amount of methyl mercapto-acetate used contained 1.5 times the theoretical amount of sulfur necessary to convert W and Co into WS 2 and CoS, respectively.
the desulfurization percentage with Catalyst-20 was 82.1%.
Catalyst-21 was prepared in the same manner as Example 3, except that 116.3 g of methyl 3-mercapto-propionate was used as the sulfurizing agent.
the breaking strength of Catalyst-21 was 1.5 kg/mm or more.
the molybdenum content was 15% by weight as MoO 3 and the cobalt content was 4% by weight as CoO.
the amount of methyl 3-mercapto-propionate used contained 1.5 times the theoretical amount of sulfur necessary to convert Mo and Co into MoS 2 and CoS, respectively.
the desulfurization percentage with Catalyst-21 was 81.0%.
Catalyst-22 was prepared in the same manner as Example 4, except that 116.3 g of ethyl 2-mercapto-acetate was used as the sulfurizing agent.
the breaking strength of Catalyst-22 was 1.5 kg/mm or more.
the molybdenum content was 15% by weight as MoO 3 and the cobalt content was 4% by weight as CoO.
the amount of ethyl 2-mercapto-acetate used contained 1.5 times the theoretical amount of sulfur necessary to convert Mo and Co into MoS 2 and CoS, respectively.
the desulfurization percentage with Catalyst-22 was 81.5%.
Catalyst-23 was obtained in the same manner as Example 5, except that 106.8 g of methyl mercapto-acetate was used as the sulfurizing agent.
the breaking strength of Catalyst-23 was 1.5 kg/mm or more.
the molybdenum content was 15% by weight as MoO 3
the cobalt content was 4% by weight as CoO
the phosphorus content was 3% by weight as P 2 O 5 .
the amount of methyl mercapto-acetate used contained 1.5 times the theoretical amount of sulfur necessary to convert Mo and Co into MoS 2 and CoS, respectively.
the desulfurization percentage with Catalyst-23 was 82.2%.
Catalyst-24 was obtained in the same manner as Example 8, except that 106.8 g of methyl mercapto-acetate was used as the sulfurizing agent.
the breaking strength of Catalyst-24 was 1.5 kg/mm or more.
the molybdenum content was 15% by weight as MoO 3
the cobalt content was 4% by weight as CoO
the phosphorus content was 3% by weight as P 2 O 5 .
the amount of methyl mercapto-acetate used contained 1.5 times the theoretical amount of sulfur necessary to convert Mo and Co into MoS 2 and CoS, respectively.
the desulfurization percentage with Catalyst-24 was 83.0%.
Catalyst-25 was prepared in the same manner as Example 9, except that 120.9 g of methyl 3-mercapto-propionate was used as the sulfurizing agent.
the breaking strength of Catalyst-25 was 1.5 kg/mm or more.
the molybdenum content was 15% by weight as MoO 3
the cobalt content was 4% by weight as CoO
the phosphorus content was 3% by weight as P 2 O 5 .
the amount of methyl 3-mercapto-propionate used contained 1.5 times the theoretical amount of sulfur necessary to convert Mo and Co into MoS 2 and CoS, respectively.
the desulfurization percentage with Catalyst-25 was 82.0%.
Catalyst-26 was prepared in the same manner as Example 5, except that 120.9 g of methyl 3-mercapto-propionate was used as the sulfurizing agent.
the breaking strength of Catalyst-26 was 1.5 kg/mm or more.
the molybdenum content was 15% by weight as MoO 3
the cobalt content was 4% by weight as CoO
the phosphorus content was 3% by weight as P 2 O 5 .
the amount of methyl 3-mercapto-propionate used contained 1.5 times the theoretical amount of sulfur necessary to convert Mo and Co into MoS 2 and CoS, respectively.
the desulfurization percentage with Catalyst-26 was 81.1%.
Catalyst-27 was prepared in the same manner as Example 8, except that 120.9 g of methyl 3-mercapto-propionate was used as the sulfurizing agent.
the breaking strength of Catalyst-27 was 1.5 kg/mm or more.
the molybdenum content was 15% by weight as MoO 2
the cobalt content was 4% by weight as CoO
the phosphorus content was 3% by weight as P 2 O 5 .
the amount of methyl 3-mercapto-propionate used contained 1.5 times the theoretical amount of sulfur necessary to convert Mo and Co into MoS 2 and CoS, respectively.
the desulfurization percentage with Catalyst-27 was 81.5%.
Catalyst-28 was prepared in the same manner as Example 12, except that 151.6 g of methyl mercapto-acetate was used as the sulfurizing agent.
the breaking strength of Catalyst-28 was 1.5 kg/mm or more.
the molybdenum content was 20% by weight as MoO 3
the nickel content was 4% by weight as NiO
the phosphorus content was 6.5% by weight as P 2 O 5 .
the amount of methyl mercapto-acetate used contained 1.5 times the theoretical amount of sulfur necessary to convert Mo and Ni into MoS 2 and NiS, respectively.
the desulfurization percentage with Catalyst-28 was 79.0%.
Catalyst-29 was prepared in the same manner as Example 13, except that 106.8 g of methyl mercapto-acetate was used as the sulfurizing agent.
the breaking strength of Catalyst-29 was 1.5 kg/mm or more.
the molybdenum content was 15% by weight as MoO 3
the cobalt content was 4% by weight as CoO
the phosphorus content was 3% by weight as P 2 O 5 .
the amount of methyl mercapto-acetate used contained 1.5 times the theoretical amount of sulfur necessary to convert Mo and Co into MoS 2 and CoS, respectively.
the desulfurization percentage with Catalyst-29 was 81.8%.
Catalyst-30 was prepared in the same manner as Example 14, except that 120.9 g of ethyl 2-mercapto-acetate was used as the sulfurizing agent.
the breaking strength of Catalyst-30 was 1.5 kg/mm or more.
the molybdenum content was 15% by weight as MoO 3 and the cobalt content was 4% by weight as CoO and the phosphorus content was 3% by weight as P 2 O 5 .
the amount of ethyl 2-mercapto-acetate used contained 1.5 times the theoretical amount of sulfur necessary to convert Mo and Co into MoS 2 and CoS, respectively.
the desulfurization percentage with Catalyst-30 was 81.8% by weight.
Catalyst-31 was prepared in the same manner as Example 15, except that 205.5 g of 2-ethylhexyl mercapto-acetate was used as the sulfurizing agent.
the breaking strength of Catalyst-31 was 1.5 kg/mm or more.
the molybdenum content was 15% by weight as MoO 3
the cobalt content was 4% by weight as CoO
the phosphorus content was 3% by weight as P 2 O 5 .
the amount of 2-ethylhexyl mercapto-acetate used contained 1.5 times the theoretical amount of sulfur necessary to convert Mo and Co into MoS 2 and CoS, respectively.
the desulfurization percentage with Catalyst-31 was 81.2%.
Catalyst-32 was prepared in the same manner as Example 16, except that 120.9 g of methyl 3-mercapto-propionate was used as the sulfurizing agent.
the breaking strength of Catalyst-32 was 1.5 kg/mm or more.
the molybdenum content was 15% by weight as MoO 3
the cobalt content was 4% by weight as CoO
the phosphorus content was 3% by weight as P 2 O 5 .
the amount of methyl 3-mercapto-propionate used contained 1.5 times the theoretical amount of sulfur necessary to convert Mo and Co into MoS 2 and CoS, respectively.
the desulfurization percentage with Catalyst-32 was 81.2%.
Catalyst-33 was obtained in the same manner as Example 17, except that 106.8 g of methyl mercapto-acetate was used as the sulfurizing agent.
the breaking strength of Catalyst-33 was 1.5 kg/mm or more.
the molybdenum content was 15% by weight as MoO 3
the cobalt content was 4% by weight as CoO
the phosphorus content was 3% by weight as P 2 O 5 .
the amount of methyl mercapto-acetate used contained 1.5 times the theoretical amount of sulfur necessary to convert Mo and Co into MoS 2 and CoS, respectively.
the desulfurization percentage with Catalyst-33 was 81.9%.
the breaking strength of Catalyst-34 was 1.5 kg/mm or more.
the molybdenum content was 15% by weight as MoO 3
the cobalt content was 4% by weight as CoO
the phosphorus content was 3% by weight as P 2 O 5 .
the amount of methyl 3-mercapto-propionate used contained 1.5 times the theoretical amount of sulfur necessary to convert Mo and Co into MoS 2 and CoS, respectively.
the desulfurization percentage with Catalyst-34 was 80.9%.
Catalyst-35 was prepared in the same manner as Example 1, except that 75.2 g of thioacetic acid was used as the sulfurizing agent.
the breaking strength of Catalyst-35 was 1.5 kg/mm or more.
the molybdenum content was 15% by weight as MoO 3 and the cobalt content was 4% by weight as CoO.
the amount of thioacetic acid used contained 1.5 times the theoretical amount of sulfur necessary to convert Mo and Co into MoS 2 and CoS, respectively.
the desulfurization percentage with Catalyst-35 was 82.8%.
Catalyst-36 was prepared in the same manner as Example 2, except that 52.3 g of thioacetic acid was used as the sulfurizing agent.
the breaking strength of Catalyst-36 was 1.5 kg/mm or more.
the tungsten content was 15% by weight as WO 3 and the cobalt content was 4% by weight as CoO.
the amount of thioacetic acid used contained 1.5 times the theoretical amount of sulfur necessary to convert W and Co into WS 2 and CoS, respectively.
the desulfurization percentage of Catalyst-36 was 82.0%.
Catalyst-37 was prepared in the same manner as Example 3, except that 75.2 g of thioacetic acid was used as the sulfurizing agent.
the breaking strength of Catalyst-37 was 1.5 kg/mm or more.
the molybdenum content was 15% by weight as MoO 3 and the cobalt content was 4% by weight as CoO.
the amount of thioacetic acid used contained 1.5 times the theoretical amount of sulfur necessary to convert Mo and Co into MoS 2 and CoS, respectively.
the desulfurization percentage of Catalyst-37 was 82.3%.
Catalyst-38 was prepared in the same manner as Example 4, except that 133.6 g of thiobenzoic acid was used as the sulfurizing agent.
the breaking strength of Catalyst-38 was 1.5 kg/mm or more.
the molybdenum content was 15% by weight as MoO 3 and the cobalt content was 4% by weight as CoO.
the amount of thiobenzoic acid used contained 1.5 times the theoretical amount of sulfur necessary to convert Mo and Co into MoS 2 and CoS, respectively.
the desulfurization percentage with Catalyst-38 was 81.9%.
Catalyst-39 was prepared in the same manner as Example 5, except that 78.2 g of thioacetic acid was used as the sulfurizing agent.
the breaking strength of Catalyst-39 was 1.5 kg/mm or more. 10 Regarding the active metal content in Catalyst-39, the molybdenum content was 15% by weight as MoO 3 , the cobalt content was 4% by weight as CoO and the phosphorus content was 3% by weight as P 2 O 5 . The amount of thioacetic acid used contained 1.5 times the theoretical amount of sulfur necessary to convert Mo and Co into MoS 2 and CoS, respectively.
the desulfurization percentage with Catalyst-39 was 83.0%.
Catalyst-40 was prepared in the same manner as Example 8, except that 78.2 g of thioacetic acid was used as the sulfurizing agent.
the breaking strength of Catalyst-40 was 1.5 kg/mm or more.
the molybdenum content was 15% by weight as MoO 3
the cobalt content was 4% by weight as CoO
the phosphorus content was 3% by weight as P 2 O 5 .
the amount of thioacetic acid used contained 1.5 times the theoretical amount of sulfur necessary to convert Mo and Co into MoS 2 and CoS, respectively.
the desulfurization percentage with Catalyst-40 was 83.6%.
Catalyst-41 was prepared in the same manner as Example 9, except that 139.0 g of thiobenzoic acid was used as the sulfurizing agent.
the breaking strength of Catalyst-41 was 1.5 kg/mm or more.
the molybdenum content was 15% by weight as MoO 3
the cobalt content was 4% by weight as CoO
the phosphorus content was 3% by weight as P 2 O 5 .
the amount of thiobenzoic acid used contained 1.5 times the theoretical amount of sulfur necessary to convert Mo and Co into MoS 2 and CoS, respectively.
the desulfurization percentage with Catalyst-41 was 85.8%.
Catalyst-42 was prepared in the same manner as Example 5, except that 139.0 g of thiobenzoic acid was used as the sulfurizing agent.
the breaking strength of Catalyst-42 was 1.5 kg/mm or more.
the molybdenum content was 15% by weight as MoO 3
the cobalt content was 4% by weight as CoO
the phosphorus content was 3% by weight as P 2 O 5 .
the amount of thiobenzoic acid used contained 1.5 times the theoretical amount of sulfur necessary to convert Mo and Co into MoS 2 and CoS, respectively.
the desulfurization percentage with Catalyst-42 was 83.8%.
Catalyst-43 was prepared in the same manner as Example 8, except that 139.0 g of thiobenzoic acid was used as the sulfurizing agent.
the breaking strength of Catalyst-43 was 1.5 kg/mm or more.
the molybdenum content was 15% by weight as MoO 3
the cobalt content was 4% by weight as CoO
the phosphorus content was 3% by weight as P 2 O 5 .
the amount of thiobenzoic acid used contained 1.5 times the theoretical amount of sulfur necessary to convert Mo and Co into MoS 2 and CoS, respectively.
the desulfurization percentage with Catalyst-43 was 84.2%.
Catalyst-44 was prepared in the same manner as Example 13, except that 110.9 g of thioacetic acid was used as the sulfurizing agent.
the breaking strength of Catalyst-44 was 1.5 kg/mm or more.
the molybdenum content was 20% by weight as MoO 3
the nickel content was 4% by weight as NiO
the phosphorus content was 6.5% by weight as P 2 O 5 .
the amount of thioacetic acid used contained 1.5 times the theoretical amount of sulfur necessary to convert Mo and Ni into MoS 2 and NiS, respectively.
the desulfurization percentage with Catalyst-44 was 80.5%.
Catalyst-45 was prepared in the same manner as Example 13, except that 78.2 g of thioacetic acid was used as the sulfurizing agent.
the breaking strength of Catalyst-45 was 1.5 kg/mm or more.
the molybdenum content was 15% by weight as MoO 3
the cobalt content was 4% by weight as CoO
the phosphorus content was 3% by weight as P 2 O 5 .
the amount of thioacetic acid used contained 1.5 times the theoretical amount of sulfur necessary to convert Mo and Co into MoS 2 and CoS, respectively.
the desulfurization percentage with Catalyst-45 was 81.5%.
Catalyst-46 was prepared in the same manner as Example 14, except that 139.0 g of thiobenzoic acid was used as the sulfurizing agent.
the breaking strength of Catalyst-46 was 1.5 kg/mm or more.
the molybdenum content was 15% by weight as MoO 3
the cobalt content was 4% by weight as CoO
the phosphorus content was 3% by weight as P 2 O 5 .
the amount of thiobenzoic acid used contained 1.5 times the theoretical amount of sulfur necessary to convert Mo and Co into MoS 2 and CoS, respectively.
the desulfurization percentage with Catalyst-46 was 83.1%.
Catalyst-47 was prepared in the same manner as Example 15, except that 78.2 g of thioacetic acid was used as the sulfurizing agent.
the breaking strength of Catalyst-47 was 1.5 kg/mm or more.
the molybdenum content was 15% by weight as MoO 3
the cobalt content was 4% by weight as CoO
the phosphorus content was 3% by weight as P 2 O 5 .
the amount of thioacetic acid used contained 1.5 times the theoretical amount of sulfur necessary to convert Mo and Co into MoS 2 and CoS, respectively.
the desulfurization percentage with Catalyst-47 was 82.5%.
Catalyst-48 was prepared in the same manner as Example 16, except that 78.2 g of thioacetic acid was used as the sulfurizing agent.
the breaking strength of Catalyst-48 was 1.5 kg/mm or more.
the molybdenum content was 15% by weight as MoO 3
the cobalt content was 4% by weight as CoO
the phosphorus content was 3% by weight as P 2 O 5 .
the amount of thioacetic acid used contained 1.5 times the theoretical amount of sulfur necessary to convert Mo and Co into MoS 2 and CoS, respectively.
the desulfurization percentage with Catalyst-48 was 82.5%.
Catalyst-49 was prepared in the same manner as Example 17, except that 78.2 g of thioacetic acid was used as the sulfurizing agent.
the breaking strength of Catalyst-49 was 1.5 kg/mm or more.
the molybdenum content was 15% by weight as MoO 3
the cobalt content was 4% by weight as CoO
the phosphorus content was 3% by weight as P 2 O 5 .
the amount of thioacetic acid used contained 1.5 times the theoretical amount of sulfur necessary to convert Mo and Co into MoS 2 and CoS, respectively.
the desulfurization percentage with Catalyst-49 was 82.8%.
Catalyst-50 was prepared in the same manner as Example 18, except that 78.2 g of thioacetic acid was used as the sulfurizing agent.
the breaking strength of Catalyst-50 was 1.5 kg/mm or more.
the molybdenum content was 15% by weight as MoO 3
the cobalt content was 4% by weight as CoO
the phosphorus content was 3% by weight as P 2 O 5 .
the amount of thioacetic acid used contained 1.5 times the theoretical amount of sulfur necessary to convert Mo and Co into MoS 2 and CoS, respectively.
the desulfurization percentage with Catalyst-50 was 82.5%.
Catalyst-51 was prepared in the same manner as Example 1, except that 74.6 g of 2-aminoethanethiol was used as the sulfurizing agent.
the breaking strength of Catalyst-51 was 1.5 kg/mm or more.
the molybdenum content was 15% by weight as MoO 3 and the cobalt content was 4% by weight as CoO.
the amount of 2-aminoethanethiol used contained 1.5 times the theoretical amount of sulfur necessary to convert Mo and Co into MoS 2 and CoS, respectively.
the desulfurization percentage with Catalyst-51 was 81.8%.
Catalyst-52 was prepared in the same manner as Example 2, except that 52.1 g of 2-aminoethanethiol was used as the sulfurizing agent.
the breaking strength of Catalyst-52 was 1.5 kg/mm or more.
the tungsten content was 15% by weight as WO 3 and the cobalt content was 4% by weight as CoO.
the amount of 2-aminoethanethiol used contained 1.5 times the theoretical amount of sulfur necessary to convert S and Co into SW 2 and CoS, respectively.
the desulfurization percentage with Catalyst-52 was 81.5%.
Catalyst-53 was prepared in the same manner as Example 3, except that 74.6 g of 2-aminoethanethiol was used as the sulfurizing agent.
the breaking strength of Catalyst-53 was 1.5 kg/mm or more.
the molybdenum content was 15% by weight as MoO 3 and the cobalt content was 4% by weight as CoO.
the amount of 2-aminoethanethiol used contained 1.5 times the theoretical amount of sulfur necessary for converting Mo and Co into MoS 2 and CoS, respectively.
the desulfurization percentage with Catalyst-53 was 81.5%.
Catalyst-54 was prepared in the same manner as Example 4, except that 121.2 g of 4-aminothiophenol was used as the sulfurizing agent.
the breaking strength of Catalyst-54 was 1.5 kg/mm or more.
the molybdenum content was 15% by weight as MoO 3 and the cobalt content was 4% by weight as CoO.
the amount of 4-aminothiophenol used contained 1.5 times the theoretical amount of sulfur necessary to convert Mo and Co into MoS 2 and CoS, respectively.
the desulfurization percentage of Catalyst-54 was 81.3%.
Catalyst-55 was prepared in the same manner as Example 5, except that 77.6 g of 2-aminoethanethiol was used as the sulfurizing agent.
the breaking strength of Catalyst-55 was 1.5 kg/mm or more.
the molybdenum content was 15% by weight as MoO 3
the cobalt content was 4% by weight
the phosphorus content was 3% by weight as P 2 O 5 .
the amount of 2-aminoethanethiol used contained 1.5 times the theoretical amount of sulfur necessary to convert Mo and Co into MoS 2 and CoS, respectively.
the desulfurization percentage with Catalyst-55 was 81.8%.
Catalyst-56 was prepared in the same manner as Example 8, except that 77.6 g of 2-aminoethanethiol was used as the sulfurizing agent.
the breaking strength of Catalyst-56 was 1.5 kg/mm or more.
the molybdenum content was 15% by weight as MoO 2
the cobalt content was 4% by weight as CoO
the phosphorus content was 3% by weight as P 2 O 5 .
the amount of 2-aminoethanethiol used contained 1.5 times the sulfur necessary to convert Mo and Co into MoS 2 and CoS, respectively.
the desulfurization percentage with Catalyst-56 was 82.5%.
Catalyst-57 was prepared in the same manner as Example 9, except that 125.9 g of 4-aminothiophenol was used as the sulfurizing agent.
the breaking strength of Catalyst-57 was 1.5 kg/mm or more.
the molybdenum content was 15% by weight as MoO 3
the cobalt content was 4% by weight as CoO
the phosphorus content was 3% by weight as P 2 O 5 .
the amount of 4-aminothiophenol used contained 1.5 times the theoretical amount of sulfur necessary to convert Mo and Co into MoS 2 and CoS, respectively.
the desulfurization percentage with Catalyst-57 was 83.8%.
Catalyst-58 was prepared in the same manner as Example 5, except that 125.9 g of 4-aminothiophenol was used as the sulfurizing agent.
the breaking strength of Catalyst-58 was 1.5 kg/mm or more.
the molybdenum content was 15% by weight as MoO 3
the cobalt content was 4% by weight as CoO
the phosphorus content was 3% by weight as P 2 O 5 .
the amount of 4-aminothiophenol used contained 1.5 times the theoretical amount of sulfur necessary to convert Mo and Co into MoS 2 and CoS, respectively.
the desulfurization percentage with Catalyst-58 was 82.6%.
Catalyst-59 was prepared in the same manner as Example 8, except that 125.9 g of 4-aminothiophenol was used as the sulfurizing agent.
the breaking strength of Catalyst-59 was 1.5 kg/mm or more.
the molybdenum content was 15% by weight as MoO 3
the cobalt content was 4% by weight as CoO
the phosphorus content was 3% by weight as P 2 O 5 .
the amount of 4-aminothiophenol used contained 1.5 times the theoretical amount of sulfur necessary to convert Mo and Co into MoS 2 and CoS, respectively.
the desulfurization percentage with Catalyst-59 was 83.5%.
Catalyst-60 was prepared in the same manner as Example 12, except that 110.1 g of 2-aminoethanethiol was used as the sulfurizing agent.
the breaking strength of Catalyst-60 was 1.5 kg/mm or more.
the molybdenum content was 20% by weight as MoO 3
the nickel content was 4% by weight as NiO
the phosphorus content was 6.5% by weight as P 2 O 5 .
the amount of 2-aminoethanethiol used contained 1.5 times the theoretical amount of sulfur necessary to convert Mo and Ni into MoS 2 and NiS, respectively.
the desulfurization percentage with Catalyst-60 was 77.8%.
Catalyst-61 was prepared in the same manner as Example 13, except that 77.6 g of 2-aminoethanethiol was used as the sulfurizing agent.
the breaking strength of Catalyst-61 was 1.5 kg/mm or more.
the molybdenum content was 15% by weight as MoO 3
the cobalt content was 4% by weight as CoO
the phosphorus content was 3% by weight as P 2 O 5 .
the amount of 2-aminoethanethiol used contained 1.5 times the theoretical amount of sulfur necessary to convert Mo and Co into MoS 2 and CoS, respectively.
the desulfurization percentage with Catalyst-61 was 82.0%.
Catalyst-62 was prepared in the same manner as Example 14, except that 125.9 g of 4-aminothiophenol was used as the sulfurizing agent.
the breaking strength of Catalyst-62 was 1.5 kg/mm or more.
the molybdenum content was 15% by weight as MoO 3
the cobalt content was 4% by weight as CoO
the phosphorus content was 3% by weight as P 2 O 5 .
the amount of 4-aminothiophenol used contained 1.5 times the theoretical amount of sulfur necessary to convert Mo and Co into MoS 2 and CoS, respectively.
the desulfurization percentage with Catalyst-62 was 83.2%.
Catalyst-63 was prepared in the same manner as Example 15, except that 77.6 g of 2-aminoethanethiol was used as the sulfurizing agent.
the breaking strength of Catalyst-63 was 1.5 kg/mm or more.
the molybdenum content was 15% by weight as MoO 3
the cobalt content was 4% by weight as CoO
the phosphorus content was 3% by weight as P 2 O 5 .
the amount of 2-aminoethanethiol used contained 1.5 times the theoretical amount of sulfur necessary to convert Mo and Co into MoS 2 and CoS, respectively.
the desulfurization percentage with Catalyst-63 was 81.8%.
Catalyst-64 was prepared in the same manner as Example 16, except that 77.6 g of 2-aminoethanethiol was used as the sulfurizing agent.
the breaking strength of Catalyst-64 was 1.5 kg/mm or more.
the molybdenum content was 15% by weight as MoO 3
the cobalt content was 4% by weight as CoO
the phosphorus content was 3% by weight as P 2 O 5 .
the amount of 2-aminoethanethiol used contained 1.5 times the theoretical amount of sulfur necessary to convert Mo and Co into MoS 2 and CoS, respectively.
the desulfurization percentage with Catalyst-64 was 81.9%.
Catalyst-65 was prepared in the same manner as Example 17, except that 77.6 g of 2-aminoethanethiol was used as the sulfurizing agent.
the breaking strength of Catalyst-65 was 1.5 kg/mm or more.
the molybdenum content was 15% by weight as MoO 3
the cobalt content was 4% by weight as CoO
the phosphorus content was 3% by weight as P 2 O 5 .
the amount of 2-aminoethanethiol used contained 1.5 times the theoretical amount of sulfur necessary to convert Mo and Co into MoS 2 and CoS, respectively.
the desulfurization percentage with Catalyst-65 was 81.6%.
Catalyst-66 was prepared in the same manner as Example 18, except that 77.6 g of 2-aminoethanethiol was used as the sulfurizing agent.
the breaking strength of Catalyst-66 was 1.5 kg/mm or more.
the molybdenum content was 15% by weight as MoO 3
the cobalt content was 4% by weight as CoO
the phosphorus content was 3% by weight as P 2 O 5 .
the amount of 2-aminoethanethiol used contained 1.5 times the theoretical amount of sulfur necessary to convert Mo and Co into MoS 2 and CoS, respectively.
the desulfurization percentage with Catalyst-66 was 81.5%.
Catalyst-67 was prepared in the same manner as Example 1, except that 45.5 g of ethanedithiol was used as the sulfurizing agent.
the breaking strength of Catalyst-67 was 1.5 kg/mm or more.
the molybdenum content was 15% by weight as MoO 3 and the cobalt content was 4% by weight as CoO.
the amount of ethanedithiol used contained 1.5 times the theoretical amount of sulfur necessary to convert Mo and Co into MoS 2 and CoS, respectively.
the desulfurization percentage with Catalyst-67 was 86.0%.
Catalyst-68 was prepared in the same manner as Example 2, except that 31.8 g of ethanedithiol was used as the sulfurizing agent.
the breaking strength of Catalyst-68 was 1.5 kg/mm or more.
the tungsten content in Catalyst-68 was 15% by weight as WO 3 and the cobalt content was 4% by weight as CoO.
the amount of ethanedithiol used contained 1.5 times the theoretical amount of sulfur necessary to convert W and Co into WS 2 and CoS, respectively.
the desulfurization percentage with Catalyst-68 was 84.5%.
Catalyst-69 was prepared in the same manner as Example 1, except that 76.5 g of 2-mercaptoethanol was used as the sulfurizing agent.
the breaking strength of Catalyst-69 was 1.5 kg/mm or more.
the molybdenum content was 15% by weight as MoO 3 and the cobalt content was 4% by weight as CoO.
the amount of 2-mercaptoethanol used contained 1.5 times the theoretical amount of sulfur necessary to convert Mo and Co into MoS 2 and CoS, respectively.
the desulfurization percentage with Catalyst-69 was 87.0%.
Catalyst-70 was prepared in the same manner as Example 2, except that 52.8 g of 2-mercaptoethanol was used as the sulfurizing agent.
the breaking strength of Catalyst-70 was 1.5 kg/mm or more.
the tungsten content was 15% by weight as WO 3 and the cobalt content was 4% by weight as CoO.
the amount of 2-mercaptoethanol used contained 1.5 times the theoretical amount of sulfur necessary to convert W and Co into WS 2 and CoS, respectively.
the desulfurization percentage with Catalyst-70 was 86.3%.
Catalyst-71 was prepared in the same manner as Example 3, except that 45.5 g of ethanedithiol was used as the sulfurizing agent.
the breaking strength of Catalyst-71 was 1.5 kg/mm or more.
the molybdenum content was 15% by weight as MoO 3 and the cobalt content was 4% by weight as CoO.
the amount of ethanedithiol used contained 1.5 times the theoretical amount of sulfur necessary to convert Mo and Co into MoS 2 and CoS, respectively.
the desulfurization percentage with Catalyst-71 was 85.0%.
Catalyst-72 was prepared in the same manner as Example 3, except that 104.6 g of 3-mercapto-1,2-propanediol was used as the sulfurizing agent.
the breaking strength of Catalyst-72 was 1.5 kg/mm or more.
the molybdenum content was 15% by weight as MoO 3 and the cobalt content was 4% by weight as CoO.
the amount of 3-mercapto-1,2-propanediol used contained 1.5 times the theoretical amount of sulfur necessary to convert Mo and Co into MoS 2 and CoS, respectively.
the desulfurization percentage with Catalyst-72 was 84.0%.
Catalyst-73 was prepared in the same manner as Example 4, except that 59.1 g of 1,4-butanedithiol was used as the sulfurizing agent.
the breaking strength of Catalyst-73 was 1.5 kg/mm or more.
the molybdenum content was 15% by weight as MoO 3 and the cobalt content was 4% by weight as CoO.
the amount of 1,4-butanedithiol used contained 1.5 times the theoretical amount of sulfur necessary to convert Mo and Co into MoS 2 and CoS, respectively.
the desulfurization percentage with Catalyst-73 was 83.5%.
Catalyst-74 was prepared in the same manner as Example 4, except that 122.0 g of 4-mercaptophenol was used as the sulfurizing agent.
the breaking strength of Catalyst-74 was 1.5 kg/mm or more.
the molybdenum content was 15% by weight as MoO 3 and the cobalt content was 4% by weight as CoO.
the amount of 4-mercaptophenol used contained 1.5 times the theoretical amount of sulfur necessary to convert Mo and Co into MoS 2 and CoS, respectively.
the desulfurization percentage with Catalyst-74 was 84.0%.
Catalyst-75 was prepared in the same manner as Example 5, except that 47.3 g of ethanedithiol was used as the sulfurizing agent.
the breaking strength of Catalyst-75 was 1.5 kg/mm or more.
the molybdenum content was 15% by weight as MoO 3
the cobalt content was 4% by weight as CoO
the phosphorus content was 3% by weight as P 2 O 5 .
the amount of ethanedithiol used contained 1.5 times the theoretical amount of sulfur necessary to convert Mo and Co into MoS 2 and CoS, respectively.
the desulfurization percentage with Catalyst-75 was 87.0%.
Catalyst-76 was prepared in the same manner as Example 8, except that 61.4 g of 1,4-butanedithiol was used as the sulfurizing agent.
the breaking strength of Catalyst-76 was 1.5 kg/mm or more.
the molybdenum content was 15% by weight as MoO 3
the cobalt content was 4% by weight
the phosphorus content was 3% by weight as P 2 O 5 .
the amount of 1,4-butanedithiol used contained 1.5 times the theoretical amount of sulfur necessary to convert Mo and Co into MoS 2 and CoS, respectively.
the desulfurization percentage with Catalyst-76 was 86.3%.
Catalyst-77 was prepared in the same manner as Example 9, except that 78.6 g of 2-mercaptoethanol was used as the sulfurizing agent.
the breaking strength of Catalyst-77 was 1.5 kg/mm or more.
the molybdenum content was 15% by weight as MoO 3
the cobalt content was 4% by weight as CoO
the phosphorus content was 3% by weight as P 2 O 5 .
the amount of 2-mercaptoethanol used contained 1.5 times the theoretical amount of sulfur necessary to convert Mo and Co into MoS 2 and CoS, respectively.
the desulfurization percentage with Catalyst-77 was 88.0%.
Catalyst-78 was prepared in the same manner as Example 5, except that 126.9 g of 4-mercaptophenol was used as the sulfurizing agent.
the breaking strength of Catalyst-78 was 1.5 kg/mm or more.
the molybdenum content was 15% by weight as MoO 3
the cobalt content was 4% by weight as CoO
the phosphorus content was 3% by weight as P 2 O 5 .
the amount of 4-mercaptophenol used contained 1.5 times the theoretical amount of sulfur necessary to convert Mo and Co into MoS 2 and CoS, respectively.
the desulfurization percentage with Catalyst-78 was 84.8%.
Catalyst-79 was prepared in the same manner as Example 8, except that 108.9 g of 3-mercapto-1,2-propanediol was used as the sulfurizing agent.
the breaking strength of Catalyst-79 was 1.5 kg/mm or more.
the molybdenum content was 15% by weight as MoO 3
the cobalt content was 4% by weight as CoO
the phosphorus content was 3% by weight as P 2 O 5 .
the amount of 3-mercapto-1,2-propanediol used contained 1.5 times the theoretical amount of sulfur necessary to convert Mo and Co into MoS 2 and CoS, respectively.
the desulfurization percentage with Catalyst-79 was 85.0%.
Catalyst-80 was prepared in the same manner as Example 12, except that 67.2 g of ethanedithiol was used as the sulfurizing agent.
the breaking strength of Catalyst-80 was 1.5 kg/mm or more.
the molybdenum content was 20% by weight as MoO 3
the nickel content was 4% by weight as NiO
the phosphorus content was 6.5% by weight as P 2 O 5 .
the amount of ethanedithiol used contained 1.5 times the theoretical amount of sulfur necessary to convert Mo and Ni into MoS 2 and NiS, respectively.
the desulfurization percentage with Catalyst-80 was 83.7%.
Catalyst-81 was prepared in the same manner as Example 12, except that 111.6 g of 2-mercaptoethanol was used as the sulfurizing agent.
the breaking strength of Catalyst-81 was 1.5 kg/mm or more.
the molybdenum content was 20% by weight as MoO 3
the nickel content was 4% by weight as NiO
the phosphorus content was 6.5% by weight as P 2 O 5 .
the amount of 2-mercaptoethanol used contained 1.5 times the theoretical amount of sulfur necessary to convert Mo and Ni into MoS 2 and NiS, respectively.
the desulfurization percentage with Catalyst-81 was 82.0%.
Catalyst-82 was obtained in the same manner as Example 8, except that 126.9 g of 4-mercaptophenol was used as the sulfurizing agent.
the molybdenum content was 15% by weight as MoO 2
the cobalt content was 4% by weight as CoO
the phosphorus content was 3% by weight as P 2 O 5 .
the amount of 4-mercaptophenol used contained 1.5 times the theoretical amount of sulfur necessary to convert Mo and Co into MoS 2 and CoS, respectively.
the desulfurization percentage with Catalyst-82 was 86.7%.
Catalyst-83 was prepared in the same manner as Example 8, except that 78.6 g of 2-mercaptoethanol was used as the sulfurizing agent.
the breaking strength of Catalyst-83 was 1.5 kg/mm or more.
the molybdenum content was 15% by weight as MoO 3
the cobalt content was 4% by weight as CoO
the phosphorus content was 3% by weight as P 2 O 5 .
the amount of 2-mercaptoethanol used contained 1.5 times the theoretical amount of sulfur necessary to convert Mo and Co into MoS 2 and CoS, respectively.
the desulfurization percentage with Catalyst-83 was 87.6%.
the breaking strength of Catalyst-84 was 1.5 kg/mm or more.
Catalyst-85 was prepared in the same manner as Example 13, except that 47.3 g of ethanedithiol was used as the sulfurizing agent.
the breaking strength of Catalyst-85 was 1.5 kg/mm or more.
the breaking strength of Catalyst-86 was 1.5 kg/mm or more.
the molybdenum content was 15% by weight as MoO 3
the cobalt content was 4% by weight as CoO
the phosphorus content was 3% by weight as P 2 O 5 .
the amount of 2-mercaptoethanol used contained 1.5 times the theoretical amount of sulfur necessary to convert Mo and Co into MoS 2 and CoS, respectively.
the desulfurization percentage with Catalyst-86 was 85.0%.
Catalyst-87 was prepared in the same manner as Example 14, except that 61.4 g of 4-butanedithiol was used as the sulfurizing agent.
the breaking strength of Catalyst-87 was 1.5 kg/mm or more.
the molybdenum content was 15% by weight as MoO 3
the cobalt content was 4% by weight as CoO
the phosphorus content was 3% by weight as P 2 O 5 .
the amount of 4-butanedithiol used contained 1.5 times the theoretical amount of sulfur necessary to convert Mo and Co into MoS 2 and CoS, respectively.
the desulfurization percentage with Catalyst-87 was 85.3%.
Catalyst-88 was prepared in the same manner as Example 15, except that 108.9 g of 3-mercapto-1,2-propanediol was used as the sulfurizing agent.
the breaking strength of Catalyst-88 was 1.5 kg/mm or more.
the molybdenum content was 15% by weight as MoO 3
the cobalt content was 4% by weight as CoO
the phosphorus content was 3% by weight as P 2 O 5 .
the amount of 3-mercapto-1,2-propanediol used contained 1.5 times the theoretical amount of sulfur necessary to convert Mo and Co into MoS 2 and CoS, respectively.
the desulfurization percentage with Catalyst-88 was 83.8%.
Catalyst-89 was obtained in the same manner as Example 16, except that 126.9 g of 4-mercaptophenol was used as the sulfurizing agent.
the breaking strength of Catalyst-89 was 1.5 kg/mm or more.
the molybdenum content was 15% by weight as MoO 3
the cobalt content was 4% by weight as CoO
the phosphorus content was 3% by weight as P 2 O 5 .
the amount of 4-mercaptophenol used contained 1.5 times the theoretical amount of sulfur necessary to convert Mo and Co into MoS 2 and CoS, respectively.
the desulfurization percentage with Catalyst-89 was 84.8%.
Catalyst-90 was prepared in the same manner as Example 17, except that 78.6 g of 2-mercaptoethanol was used as the sulfurizing agent.
the breaking strength of Catalyst-90 was 1.5 kg/mm or more.
the molybdenum content was 15% by weight as MoO 3
the cobalt content was 4% by weight as CoO
the phosphorus content was 3% by weight as P 2 O 5 .
the amount of 2-mercaptoethanol used contained 1.5 times the theoretical amount of sulfur necessary to convert Mo and Co into MoS 2 and CoS, respectively.
the desulfurization percentage with Catalyst-90 was 84.5%.
Catalyst-91 was prepared in the same manner as Example 18, except that 47.3 g of ethanedithiol was used as the sulfurizing agent.
the breaking strength of Catalyst-91 was 1.5 kg/mm or more.
the molybdenum content was 15% by weight as MoO 3
the cobalt content was 4% by weight as CoO
the phosphorus content was 3% by weight as P 2 O 5 .
the amount of ethanedithiol used contained 1.5 times the theoretical amount of sulfur necessary to convert Mo and Co into MoS 2 and CoS, respectively.
the desulfurization percentage with Catalyst-91 was 87.0%.
a commercial catalyst comprising 15 wt. % of MoO 3 and 4 wt. % of CoO as carried on ⁇ -alumina (KF-742, commercial product by Nippon Ketjen Co.) was prepared.
the catalyst was presulfurized in accordance with the following conditions:
the activity of the thus-presulfurized catalyst was evaluated in the same manner as in the above-mentioned examples.
the desulfurization percentage was 82.4%.
100 g of shaped ⁇ -alumina carrier having a relative surface area of 280 m 2 /g and a pore volume of 0.75 ml/g was impregnated with 80 ml of a processing liquid prepared from 19.2 g of molybdenum trioxide, 8.2 g of cobalt carbonate having Co-content of 49.1 wt. %, 6.2 g of 85 wt. % phosphoric acid and water and dried at 110° C. for 16 hours and thereafter fired at 500° C. for 2 hours. Accordingly, a catalyst containing 15% by weight of MoO 3 , 4% by weight of CoO and 3% by weight of P 2 O 5 was obtained.
the catalyst was presulfurized in the same manner as in the above-mentioned Comparative Example 1 and the activity of the thus-presulfurized catalyst was evaluated in the same manner as in the above-mentioned examples.
the desulfurization percentage was 80.4%.
the catalysts of the present invention require neither presulfurization nor firing and can directly be applied to hydrotreatment, as they are prepared by the use of an organic compound having one or two sulfurs as a sulfurizing agent. Accordingly, the catalysts of the present invention are more economical than the conventional catalysts.

Landscapes

Chemical & Material Sciences (AREA)
Engineering & Computer Science (AREA)
Organic Chemistry (AREA)
Chemical Kinetics & Catalysis (AREA)
Oil, Petroleum & Natural Gas (AREA)
Materials Engineering (AREA)
General Chemical & Material Sciences (AREA)
Catalysts (AREA)
Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

US07/394,560 1988-08-19 1989-08-16 Catalysts for hydrotreating hydrocarbons and methods of preparing the same Expired - Lifetime US4992403A (en)

Applications Claiming Priority (10)

Application Number	Priority Date	Filing Date	Title
JP63206194A JPH0256249A (ja)	1988-08-19	1988-08-19	炭化水素の水素化処理用触媒及びその製造方法
JP63-206194		1988-08-19
JP63-225099		1988-09-08
JP63225099A JPH0271844A (ja)	1988-09-08	1988-09-08	炭化水素の水素化処理用触媒及びその製造方法
JP63229246A JPH0278441A (ja)	1988-09-13	1988-09-13	炭化水素の水素化処理用媒体及びその製造方法
JP63-229246		1988-09-13
JP63229247A JPH0278442A (ja)	1988-09-13	1988-09-13	炭化水素の水素化処理用触媒及びその製造方法
JP63-229247		1988-09-13
JP63234000A JPH0283041A (ja)	1988-09-19	1988-09-19	炭化水素の水素化処理用触媒及びその製造方法
JP63-234000		1988-09-19

Publications (1)

Publication Number	Publication Date
US4992403A true US4992403A (en)	1991-02-12

Family

ID=27529396

Family Applications (1)

Application Number	Title	Priority Date	Filing Date
US07/394,560 Expired - Lifetime US4992403A (en)	1988-08-19	1989-08-16	Catalysts for hydrotreating hydrocarbons and methods of preparing the same

Country Status (4)

Country	Link
US (1)	US4992403A (fr)
EP (1)	EP0357295B1 (fr)
CA (1)	CA1332934C (fr)
DE (1)	DE68926764T2 (fr)

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
US5017535A (en) *	1990-06-20	1991-05-21	Akzo N.V.	Process for the preparation of a presulfided and sulfided catalyst
US5162281A (en) *	1991-01-22	1992-11-10	Sumitomo Metal Mining Co. Ltd.	Method of preparing hydrotreating catalyst for hydrocarbon oil
US5468709A (en) *	1992-11-18	1995-11-21	Sumitomo Metal Mining Co., Ltd.	Catalysts for hydrotreating hydrocarbon oils and method of preparing the same
US5786293A (en) *	1996-06-17	1998-07-28	Shell Oil Company	Process for presulfiding hydrocarbon processing catalysts
US5821191A (en) *	1996-06-17	1998-10-13	Shell Oil Company	Process for presulfiding hydrocarbon processing catalysts
US6218333B1 (en)	1999-02-15	2001-04-17	Shell Oil Company	Preparation of a hydrotreating catalyst
US6281158B1 (en)	1999-02-15	2001-08-28	Shell Oil Company	Preparation of a co-containing hydrotreating catalyst precursor and catalyst
US6288006B1 (en) *	1997-01-21	2001-09-11	Elf Aquitaine Exploration Production France	Method for pre-sulphurization of catalysts
US20040112795A1 (en) *	2001-02-22	2004-06-17	Claude Brun	Method for sulphurizing hydrotreating catalysts
US20060157387A1 (en) *	2003-07-07	2006-07-20	Francis Humblot	Method for prevention of corrosion by naphthenic acids in refineries
US20070006523A1 (en) *	2005-07-05	2007-01-11	Neste Oil Oyj	Process for the manufacture of diesel range hydro-carbons
US20070010682A1 (en) *	2005-07-05	2007-01-11	Neste Oil Oyj	Process for the manufacture of diesel range hydrocarbons
US20110068045A1 (en) *	2008-05-01	2011-03-24	Intevep, S.A.	Dispersed metal sulfide-based catalysts
WO2019016375A1 (fr) *	2017-07-21	2019-01-24	Albemarle Europe Sprl	Catalyseur d'hydrotraitement avec un support contenant du titane et un additif organique contenant du soufre
WO2019016372A1 (fr) *	2017-07-21	2019-01-24	Albemarle Europe Sprl	Catalyseur d'hydrotraitement avec un entraîneur contenant du titane et un additif organique
RU2771815C2 (ru) *	2017-07-21	2022-05-12	Альбемарл Юроп Срл	Катализатор гидроочистки с титансодержащим носителем и серосодержащей органической добавкой
US12203035B2 (en)	2005-07-05	2025-01-21	Neste Oyj	Process for the manufacture of diesel range hydrocarbons

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
JPH04135643A (ja) *	1990-09-28	1992-05-11	Sumitomo Metal Mining Co Ltd	前硫化型水素化処理触媒及びその製造方法
JP3244693B2 (ja) *	1990-10-17	2002-01-07	住友金属鉱山株式会社	炭化水素油の水素化処理用触媒の製造方法
JP3244692B2 (ja) *	1990-10-17	2002-01-07	住友金属鉱山株式会社	炭化水素油の水素化処理用触媒の製造方法
JP3802106B2 (ja) †	1995-06-08	2006-07-26	日本ケッチェン株式会社	炭化水素油の水素化処理触媒とその製造方法およびその活性化方法
US6923904B1 (en)	1999-04-02	2005-08-02	Akso Nobel N.V.	Process for effecting ultra-deep HDS of hydrocarbon feedstocks
WO2001076742A1 (fr)	2000-04-11	2001-10-18	Akzo Nobel N.V.	Sulfuration en deux operations d'un catalyseur contenant un additif soufre
US6872678B2 (en)	2000-04-11	2005-03-29	Akzo Nobel N.V.	Process for activating a catalyst containing an S-containing additive
US6509291B2 (en)	2000-04-11	2003-01-21	Akzo Nobel N.V.	Process for sulfiding a catalyst containing an S-containing additive
EP1322730A1 (fr) *	2000-09-04	2003-07-02	Akzo Nobel N.V.	Processus de realisation d'hydrodesulfuration ultra profonde de charges d'hydrocarbure
US20060060510A1 (en)	2004-09-17	2006-03-23	Bhan Opinder K	High activity hydrodesulfurization catalyst, a method of making a high activity hydrodesulfurization catalyst, and a process for manufacturing an ultra-low sulfur distillate product
FR2880823B1 (fr)	2005-01-20	2008-02-22	Total France Sa	Catalyseur d'hydrotraitement, son procede de preparation et et son utilisation
WO2007059621A1 (fr)	2005-11-23	2007-05-31	Pedro Pereira-Almao	Compositions de catalyseurs ultradispersés et procédés de préparation de celles-ci
FR2936962B1 (fr) *	2008-10-10	2011-05-06	Eurecat Sa	Procede de regeneration de catalyseurs de traitement d'hydrocarbures.
FR2936961B1 (fr)	2008-10-10	2011-05-06	Eurecat Sa	Procede de regeneration de catalyseurs de traitement d'hydrocarbures.
CN102728372B (zh) *	2011-04-14	2014-06-25	中国石油化工股份有限公司	一种加氢精制催化剂的制备方法
US20180126362A1 (en) *	2015-04-24	2018-05-10	Albemarle Europe Sprl	Hydrotreating catalyst containing metal organic sulfides on doped supports

Citations (1)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
US4845068A (en) *	1987-04-22	1989-07-04	Sumitomo Metal Mining Company Limited	Catalysts for hydrotreating hydrocarbons and method of activating the same

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
US4111796A (en) *	1976-04-02	1978-09-05	Gulf Research & Development Co.	Method for presulfiding hydrodesulfurization catalysts
DE3861642D1 (de) *	1987-07-02	1991-02-28	Sumitomo Metal Mining Co	Katalysator zur wasserstoffbehandlung von kohlenwasserstoffen und methode zu dessen herstellung.

1989
- 1989-08-15 EP EP89308329A patent/EP0357295B1/fr not_active Expired - Lifetime
- 1989-08-15 DE DE68926764T patent/DE68926764T2/de not_active Expired - Fee Related
- 1989-08-16 US US07/394,560 patent/US4992403A/en not_active Expired - Lifetime
- 1989-08-16 CA CA000608541A patent/CA1332934C/fr not_active Expired - Fee Related

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
US4845068A (en) *	1987-04-22	1989-07-04	Sumitomo Metal Mining Company Limited	Catalysts for hydrotreating hydrocarbons and method of activating the same

Cited By (37)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
US5017535A (en) *	1990-06-20	1991-05-21	Akzo N.V.	Process for the preparation of a presulfided and sulfided catalyst
US5162281A (en) *	1991-01-22	1992-11-10	Sumitomo Metal Mining Co. Ltd.	Method of preparing hydrotreating catalyst for hydrocarbon oil
US5468709A (en) *	1992-11-18	1995-11-21	Sumitomo Metal Mining Co., Ltd.	Catalysts for hydrotreating hydrocarbon oils and method of preparing the same
US5786293A (en) *	1996-06-17	1998-07-28	Shell Oil Company	Process for presulfiding hydrocarbon processing catalysts
US5821191A (en) *	1996-06-17	1998-10-13	Shell Oil Company	Process for presulfiding hydrocarbon processing catalysts
US6288006B1 (en) *	1997-01-21	2001-09-11	Elf Aquitaine Exploration Production France	Method for pre-sulphurization of catalysts
US6218333B1 (en)	1999-02-15	2001-04-17	Shell Oil Company	Preparation of a hydrotreating catalyst
US6281158B1 (en)	1999-02-15	2001-08-28	Shell Oil Company	Preparation of a co-containing hydrotreating catalyst precursor and catalyst
US6290841B1 (en)	1999-02-15	2001-09-18	Shell Oil Company	Hydrotreating process using sulfur activated non-calcined catalyst
US20040112795A1 (en) *	2001-02-22	2004-06-17	Claude Brun	Method for sulphurizing hydrotreating catalysts
US7491318B2 (en) *	2003-07-07	2009-02-17	Arkema France	Method for prevention of corrosion by naphthenic acids in refineries
US20060157387A1 (en) *	2003-07-07	2006-07-20	Francis Humblot	Method for prevention of corrosion by naphthenic acids in refineries
US8278492B2 (en) *	2005-07-05	2012-10-02	Neste Oil Oyj	Process for the manufacture of diesel range hydrocarbons
US9598327B2 (en)	2005-07-05	2017-03-21	Neste Oil Oyj	Process for the manufacture of diesel range hydrocarbons
US20100287821A9 (en) *	2005-07-05	2010-11-18	Neste Oil Oyj	Process for the manufacture of diesel range hydro-carbons
US11473018B2 (en)	2005-07-05	2022-10-18	Neste Oyj	Process for the manufacture of diesel range hydrocarbons
US8022258B2 (en) *	2005-07-05	2011-09-20	Neste Oil Oyj	Process for the manufacture of diesel range hydrocarbons
US8212094B2 (en)	2005-07-05	2012-07-03	Neste Oil Oyj	Process for the manufacture of diesel range hydrocarbons
US20070006523A1 (en) *	2005-07-05	2007-01-11	Neste Oil Oyj	Process for the manufacture of diesel range hydro-carbons
US10550332B2 (en)	2005-07-05	2020-02-04	Neste Oyj	Process for the manufacture of diesel range hydrocarbons
US20070010682A1 (en) *	2005-07-05	2007-01-11	Neste Oil Oyj	Process for the manufacture of diesel range hydrocarbons
US8859832B2 (en)	2005-07-05	2014-10-14	Neste Oil Oyj	Process for the manufacture of diesel range hydrocarbons
US10800976B2 (en)	2005-07-05	2020-10-13	Neste Oyj	Process for the manufacture of diesel range hydrocarbons
US10059887B2 (en) *	2005-07-05	2018-08-28	Neste Oyj	Process for the manufacture of diesel range hydrocarbons
US12203035B2 (en)	2005-07-05	2025-01-21	Neste Oyj	Process for the manufacture of diesel range hydrocarbons
US8815765B2 (en)	2008-05-01	2014-08-26	Intevep, S.A.	Dispersed metal sulfide-based catalysts
US8551907B2 (en)	2008-05-01	2013-10-08	Intevep, S.A.	Dispersed metal sulfide-based catalysts
US20110068045A1 (en) *	2008-05-01	2011-03-24	Intevep, S.A.	Dispersed metal sulfide-based catalysts
WO2019016372A1 (fr) *	2017-07-21	2019-01-24	Albemarle Europe Sprl	Catalyseur d'hydrotraitement avec un entraîneur contenant du titane et un additif organique
CN111050904A (zh) *	2017-07-21	2020-04-21	雅宝欧洲有限责任公司	具有含钛载体和有机添加剂的加氢处理催化剂
RU2771312C2 (ru) *	2017-07-21	2022-04-29	Альбемарл Юроп Срл	Катализатор гидроочистки с титансодержащим носителем и органической добавкой
RU2771815C2 (ru) *	2017-07-21	2022-05-12	Альбемарл Юроп Срл	Катализатор гидроочистки с титансодержащим носителем и серосодержащей органической добавкой
US11420193B2 (en) *	2017-07-21	2022-08-23	Albemarle Europe Srl	Hydrotreating catalyst with a titanium containing carrier and organic additive
CN110913985A (zh) *	2017-07-21	2020-03-24	雅宝欧洲有限责任公司	具有含钛载体和含硫有机添加剂的加氢处理催化剂
US20220339614A1 (en) *	2017-07-21	2022-10-27	Albemarle Europe Srl	Hydrotreating catalyst with a titanium containing carrier and organic additive
US11524278B2 (en)	2017-07-21	2022-12-13	Albemarle Europe Srl	Hydrotreating catalyst with a titanium containing carrier and sulfur containing organic additive
WO2019016375A1 (fr) *	2017-07-21	2019-01-24	Albemarle Europe Sprl	Catalyseur d'hydrotraitement avec un support contenant du titane et un additif organique contenant du soufre

Also Published As

Publication number	Publication date
DE68926764D1 (de)	1996-08-08
EP0357295A2 (fr)	1990-03-07
EP0357295B1 (fr)	1996-07-03
DE68926764T2 (de)	1996-10-31
CA1332934C (fr)	1994-11-08
EP0357295A3 (en)	1990-03-28

Legal Events

Date	Code	Title	Description
1989-08-16	AS	Assignment	Owner name: SUMITOMO METAL MINING COMPANY LIMITED, JAPAN Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:TAKAHASHI, YASUHITO;KAWAGUCHI, TOMIO;SAKAI, SHIGERU;REEL/FRAME:005116/0127 Effective date: 19890801
1990-12-13	STCF	Information on status: patent grant	Free format text: PATENTED CASE
1993-12-08	FEPP	Fee payment procedure	Free format text: PAYOR NUMBER ASSIGNED (ORIGINAL EVENT CODE: ASPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY
1994-07-25	FPAY	Fee payment	Year of fee payment: 4
1998-08-04	FPAY	Fee payment	Year of fee payment: 8
2002-07-18	FPAY	Fee payment	Year of fee payment: 12

Publication	Publication Date	Title
US4992403A (en)	1991-02-12	Catalysts for hydrotreating hydrocarbons and methods of preparing the same
US4845068A (en)	1989-07-04	Catalysts for hydrotreating hydrocarbons and method of activating the same
US4981828A (en)	1991-01-01	Catalyst for hydrotreatment of hydrocarbons and method for production thereof
EP1322730A1 (fr)	2003-07-02	Processus de realisation d'hydrodesulfuration ultra profonde de charges d'hydrocarbure
JP2007533834A (ja)	2007-11-22	低硫黄留出油の製造方法
US5484756A (en)	1996-01-16	Hydrodesulfurization catalyst and preparation thereof
WO2001076739A1 (fr)	2001-10-18	Procede de sulfuration ex situ d'un catalyseur contenant un additif a teneur en s
JP2920255B2 (ja)	1999-07-19	水素化脱硫触媒
CA2405809C (fr)	2011-01-04	Procede d'activation d'un catalyseur comprenant un additif contenant s
JP2531728B2 (ja)	1996-09-04	炭化水素の水素化処理用触媒およびその活性化方法
JP2575168B2 (ja)	1997-01-22	炭化水素の水素化処理用触媒及びその製造方法
JPH0549342B2 (fr)	1993-07-26
JPH0549339B2 (fr)	1993-07-26
JPH0283041A (ja)	1990-03-23	炭化水素の水素化処理用触媒及びその製造方法
DE60102223T2 (de)	2005-04-14	Verfahren zur sulfidierung eines ein schwefeladditiv enthaltenden katalysators
JP2531730B2 (ja)	1996-09-04	炭化水素の水素化処理用触媒及びその製造方法
JPH0549340B2 (fr)	1993-07-26
JPH0549341B2 (fr)	1993-07-26
JPH03109945A (ja)	1991-05-09	炭化水素油の水素化処理用触媒の製造方法
JP2920256B2 (ja)	1999-07-19	水素化脱硫触媒
JPH01236945A (ja)	1989-09-21	炭化水素の水素化処理用触媒及びその製造方法
JPH01236946A (ja)	1989-09-21	炭化水素の水素化処理用触媒及びその製造方法
JPS63310642A (ja)	1988-12-19	炭化水素の水素化処理用触媒およびその活性化方法
JPH046418B2 (fr)	1992-02-05
JPH07178B2 (ja)	1995-01-11	炭化水素の水素化処理用触媒の製造方法